Microbiocidal quinoline (thio)carboxamide derivatives

ABSTRACT

Compounds of formula (I), wherein the substitutents are as defined in claim  1 . Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

The present invention relates to microbiocidal quinoline(thio)carboxamide derivatives, e.g. as active ingredients, which havemicrobiocidal activity, in particular fungicidal activity. The inventionalso relates to preparation of these quinoline (thio)carboxamidederivatives, to intermediates useful in the preparation of thesequinoline (thio)carboxamide derivatives, to the preparation of theseintermediates, to agrochemical compositions which comprise at least oneof the quinoline (thio)carboxamide derivatives, to preparation of thesecompositions and to the use of the quinoline (thio)carboxamidederivatives or compositions in agriculture or horticulture forcontrolling or preventing infestation of plants, harvested food crops,seeds or non-living materials by phytopathogenic microorganisms, inparticular fungi.

Certain fungicidal quinoline (thio)carboxamide compounds are describedin WO2004/005261.

It has now surprisingly been found that certain novel quinoline(thio)carboxamide derivatives have favourable fungicidal properties.

The present invention therefore provides compounds of formula (I)

wherein

X is O or S;

R₁ is hydrogen, halogen, methyl, methoxy or cyano;

R₂ and R₃ are each independently hydrogen, halogen, methoxy or methyl;

R₄ is hydrogen, halogen, cyano, C₁-C₄ alkoxy, C₁-C₄ alkyl, or C₃-C₄cycloalkyl, wherein the alkoxy, alkyl and cycloalkyl may be optionallysubstituted with 1 to 3 substituents independently selected fromhalogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy and C₁-C₃ alkylthio;

R₅ and R₆ are each independently selected from hydrogen, halogen, C₁-C₄alkyl, C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio and C₁-C₄haloalkylthio; or

R₅ and R₆ together with the carbon atom to which they are attachedrepresent C═O, C═NOR_(c), C₃-C₅ cycloalkyl or C₂_alkenyl, wherein thecycloalkyl may be optionally substituted with 1 to 3 substituentsindependently selected from halogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxyand C₁-C₃ alkylthio, and wherein the alkenyl may be optionallysubstituted with 1 or 2 substituents independently selected from cyano,C₁-C₄ alkyl, fluoro and chloro;

R₇ is hydrogen, cyano, —CHO, —C(═O)C₁-C₅ alkyl, —CH(═NOR_(c)),—C(═NOR_(c))C₁-C₅ alkyl, C₁-C₅ alkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkenyl,C₃-C₅ cycloalkenyl, or C₂-C₅ alkynyl, wherein the alkyl, cycloalkyl,alkenyl, alkynyl, cycloalkenyl may be optionally substituted with 1 to 4substituents independently selected from halogen, cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy, hydroxyl and C₁-C₃ alkylthio;

R₈ and R₉ are each independently selected from hydrogen, halogen, C₁-C₄alkyl and C₁-C₄ alkoxy; or

R₈ and R₉ together with the carbon atom to which they are attachedrepresent C═O, C═NOR_(c) or C₃-C₅ cycloalkyl, wherein the cycloalkyl maybe optionally substituted with 1 to 3 substituents independentlyselected from halogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy and C₁-C₃alkylthio;

each R₁₀ independently represents halogen, nitro, cyano, formyl, C₁-C₅alkyl, C₂-C₅ alkenyl, C₂-C₅ alkynyl, C₃-C₆ cycloalkyl, C₁-C₅ alkoxy,C₃-C₅ alkenyloxy, C₃-C₅ alkynyloxy, C₁-C₅ alkylthio, —C(═NOR_(c))C₁-C₅alkyl, or C₁-C₅ alkylcarbonyl, wherein the alkyl, cycloalkyl, alkenyl,alkynyl, alkoxy, alkenyloxy, alkynyloxy and alkylthio may be optionallysubstituted with 1 to 5 substituents independently selected fromhalogen, C₁-C₃ alkyl, C₁-C₃ alkoxy, cyano and C₁-C₃ alkylthio; n is 0,1, 2, 3, 4 or 5;

each R_(c) is independently selected from hydrogen, C₁-C₄ alkyl, C₂-C₄alkenyl, C₃-C₄ alkynyl, C₃-C₄ cycloalkyl(C₁-C₂)alkyl and C₃-C₄cycloalkyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl groupsmay be optionally substituted with 1 to 3 substituents independentlyselected from halogen and cyano;

R₁₁ is hydrogen, halogen, methyl, methoxy or cyano;

R₁₂ and R₁₃ are each independently selected from hydrogen, halogen,methyl, methoxy or hydroxyl;

R₁₄ is hydrogen, C₁-C₅ alkyl, C₃-C₅ cycloalkyl, C₃-C₅ alkenyl, C₃-C₅alkynyl or C₁-C₅ alkoxy wherein the alkyl, cycloalkyl, alkenyl, alkynyland alkoxy may be optionally substituted with 1 to 4 substituentsindependently selected from halogen, cyano, C₁-C₃ alkoxy, C₁-C₃alkylsulfonyl and C₁-C₃ alkylthio;

and salts, enantiomers and/or N-oxides thereof.

In a second aspect the present invention provides an agrochemicalcomposition comprising a compound of formula (I).

Compounds of formula (I) may be used to control phytopathogenicmicroorganisms. Thus, in order to control a phytopathogen a compound offormula (I), or a composition comprising a compound of formula (I),according to the invention may be applied directly to the phytopathogen,or to the locus of a phytopathogen, in particular to a plant susceptibleto attack by phytopathogens.

Thus, in a third aspect the present invention provides the use of acompound of formula (I), or a composition comprising a compound offormula (I), as described herein to control a phytopathogen.

In a further aspect the present invention provides a method ofcontrolling phytopathogens, comprising applying a compound of formula(I), or a composition comprising a compound of formula (I), as describedherein to said phytopathogen, or to the locus of said phytopathogen, inparticular to a plant susceptible to attack by a phytopathogen.

Compounds of formula (I) are particularly effective in the control ofphytopathogenic fungi.

Thus, in a yet further aspect the present invention provides the use ofa compound of formula (I), or a composition comprising a compound offormula (I), as described herein to control phytopathogenic fungi.

In a further aspect the present invention provides a method ofcontrolling phytopathogenic fungi, comprising applying a compound offormula (I), or a composition comprising a compound of formula (I), asdescribed herein to said phytopathogenic fungi, or to the locus of saidphytopathogenic fungi, in particular to a plant susceptible to attack byphytopathogenic fungi.

Where substituents are indicated as being optionally substituted, thismeans that they may or may not carry one or more identical or differentsubstituents, e.g. one to three substituents. Normally not more thanthree such optional substituents are present at the same time. Where agroup is indicated as being substituted, e.g. alkyl, this includes thosegroups that are part of other groups, e.g. the alkyl in alkylthio.

The term “halogen” refers to fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine.

Alkyl substituents (either alone or as part of a larger group, such asalkoxy-, alkylthio-) may be straight-chained or branched. Alkyl on itsown or as part of another substituent is, depending upon the number ofcarbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl,iso-butyl, sec-butyl, tert-butyl or iso-amyl.

Alkenyl substituents (either alone or as part of a larger group, eg.alkenyloxy) can be in the form of straight or branched chains, and thealkenyl moieties, where appropriate, can be of either the (E)- or(Z)-configuration. Examples are vinyl and allyl. The alkenyl groups arepreferably C₂-C₆, more preferably C₂-C₄ and most preferably C₂-C₃alkenyl groups.

Alkynyl substituents (either alone or as part of a larger group, eg.alkynyloxy) can be in the form of straight or branched chains. Examplesare ethynyl and propargyl. The alkynyl groups are preferably C₂-C₆, morepreferably C₂-C₄ and most preferably C₂-C₃ alkynyl groups.

Cycloalkyl substituents may be saturated or partially unsaturated,preferably fully saturated, and are, for example, cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl.

Haloalkyl groups (either alone or as part of a larger group, eg.haloalkyloxy) may contain one or more identical or different halogenatoms and, for example, may stand for CH₂Cl, CHCl₂, CCl₃, CH₂F, CHF₂,CF₃, CF₃CH₂, CH₃CF₂, CF₃CF₂ or CCl₃CCl₂.

Haloalkenyl groups (either alone or as part of a larger group, eg.haloalkenyloxy) are alkenyl groups, respectively, which are substitutedwith one or more of the same or different halogen atoms and are, forexample, 2,2-difluorovinyl or 1,2-dichloro-2-fluoro-vinyl.

Haloalkynyl groups (either alone or as part of a larger group, eg.haloalkynyloxy) are alkynyl groups, respectively, which are substitutedwith one or more of the same or different halogen atoms and are, forexample, 1-chloro-prop-2-ynyl.

Alkoxy means a radical —OR, where R is alkyl, e.g. as defined above.Alkoxy groups include, but are not limited to, methoxy, ethoxy,1-methylethoxy, propoxy, butoxy, 1-methylpropoxy and 2-methylpropoxy.

Cyano means a —CN group.

Amino means an —NH₂ group.

Hydroxyl or hydroxy stands for a —OH group.

Aryl groups (either alone or as part of a larger group, such as e.g.aryloxy, aryl-alkyl) are aromatic ring systems which can be in mono-,bi- or tricyclic form. Examples of such rings include phenyl, naphthyl,anthracenyl, indenyl or phenanthrenyl. Preferred aryl groups are phenyland naphthyl, phenyl being most preferred. Where an aryl moiety is saidto be substituted, the aryl moiety is preferably substituted by one tofour substituents, most preferably by one to three substituents.

Heteroaryl groups (either alone or as part of a larger group, such ase.g. heteroaryloxy, heteroaryl-alkyl) are aromatic ring systemscontaining at least one heteroatom and consisting either of a singlering or of two or more fused rings. Preferably, single rings willcontain up to three heteroatoms and bicyclic systems up to fourheteroatoms which will preferably be chosen from nitrogen, oxygen andsulfur. Examples of monocyclic groups include pyridyl, pyridazinyl,pyrimidinyl, pyrazinyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl (e.g.[1,2,4]triazolyl), furanyl, thiophenyl, oxazolyl, isoxazolyl,oxadiazolyl, thiazolyl, isothiazolyl and thiadiazolyl. Examples ofbicyclic groups include purinyl, quinolinyl, cinnolinyl, quinoxalinyl,indolyl, indazolyl, benzimidazolyl, benzothiophenyl and benzothiazolyl.Monocyclic heteroaryl groups are preferred, pyridyl being mostpreferred. Where a heteroaryl moiety is said to be substituted, theheteroaryl moiety is preferably substituted by one to four substituents,most preferably by one to three substituents.

Heterocyclyl groups or heterocyclic rings (either alone or as part of alarger group, such as heterocyclyl-alkyl) are non-aromatic ringstructures containing up to 10 atoms including one or more (preferablyone, two or three) heteroatoms selected from O, S and N. Examples ofmonocyclic groups include, oxetanyl, 4,5-dihydro-isoxazolyl, thietanyl,pyrrolidinyl, tetrahydrofuranyl, [1,3]dioxolanyl, piperidinyl,piperazinyl, [1,4]dioxanyl, imidazolidinyl, [1,3,5]oxadiazinanyl,hexahydro-pyrimidinyl, [1,3,5]triazinanyl and morpholinyl or theiroxidised versions such as 1-oxo-thietanyl and 1,1-dioxo-thietanyl.Examples of bicyclic groups include 2,3-dihydro-benzofuranyl,benzo[1,4]dioxolanyl, benzo[1,3]dioxolanyl, chromenyl, and2,3-dihydro-benzo[1,4]dioxinyl. Where a heterocyclyl moiety is said tobe substituted, the heterocyclyl moiety is preferably substituted by oneto four substituents, most preferably by one to three substituents.

The presence of one or more possible asymmetric carbon atoms in acompound of formula (I) means that the compounds may occur in opticallyisomeric forms, i.e. enantiomeric or diastereomeric forms. Alsoatropisomers may occur as a result of restricted rotation about a singlebond. Formula (I) is intended to include all those possible isomericforms and mixtures thereof. The present invention includes all thosepossible isomeric forms and mixtures thereof for a compound of formula(I). Likewise, formula (I) is intended to include all possibletautomers. The present invention includes all possible tautomeric formsfor a compound of formula (I).

In each case, the compounds of formula (I) according to the inventionare in free form, in oxidized form as a N-oxide or in salt form, e.g. anagronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms ofnitrogen containing heteroaromatic compounds. They are described forinstance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra,CRC Press, Boca Raton 1991.

Preferred values of X, R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁,R₁₂, R₁₃, R₁₄, n and R_(c) are, in any combination thereof, as set outbelow:

Preferably X is O.

Preferably R₁ is hydrogen, halogen, methyl or cyano.

More preferably R₁ is hydrogen, fluoro, chloro or methyl.

Even more preferably R₁ is hydrogen, fluoro or methyl.

More preferably still R₁ is hydrogen or fluoro.

Most preferably R₁ is fluoro.

Preferably R₂ and R₃ are each independently hydrogen, halogen or methyl.

More preferably R₂ and R₃ are each independently hydrogen, fluoro,chloro or methyl.

Even more preferably R₂ and R₃ are each independently hydrogen, fluoroor methyl.

Most preferably R₂ is hydrogen and R₃ is methyl; or R₂ is methyl and R₃is hydrogen; or R₂ and R₃ are both hydrogen.

Preferably R₄ is hydrogen, halogen, cyano, C₁-C₄ alkoxy or C₁-C₄ alkyl,wherein the alkoxy and alkyl may be optionally substituted with 1 to 2substituents independently selected from cyano, C₁-C₃ alkyl, C₁-C₃alkoxy, fluoro and chloro or 1 to 3 substituents independently selectedfrom fluoro and chloro.

More preferably R₄ is hydrogen, fluoro, C₁-C₃ alkoxy or C₁-C₃ alkyl,wherein the alkoxy and alkyl may be optionally substituted with 1 to 2substituents independently selected from cyano, C₁-C₂ alkoxy, fluoro andchloro or 1 to 3 substituents independently selected from fluoro andchloro.

Even more preferably R₄ is hydrogen, fluoro, C₁-C₃ alkoxy or C₁-C₂alkyl, wherein the alkoxy and alkyl may be optionally substituted with 1to 2 substituents independently selected from C₁-C₂ alkoxy, and fluoroor 1 to 3 fluoro substituents.

More preferably still R₄ is hydrogen or C₁-C₂ alkyl, wherein the alkylmay be optionally substituted with 1 methoxy substituent or 1 to 3fluoro substituents.

Most preferably R₄ is methyl.

Preferably R₅ and R₆ are each independently selected from hydrogen,halogen, C₁-C₃ alkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy and C₁-C₃alkylthio; or R₅ and R₆ together with the carbon atom to which they areattached represent C═O, C═NOR_(c) or C₂-alkenyl, wherein the alkenyl maybe optionally substituted with 1 or 2 substituents independentlyselected from cyano, C₁-C₃ alkyl, fluoro and chloro.

More preferably R₅ and R₆ are each independently selected from hydrogen,fluoro, chloro, C₁-C₂ alkyl, C₁-C₃ alkoxy and C₁-C₂ haloalkoxy; or R₅and R₆ together with the carbon atom to which they are attachedrepresent C═NOR_(c) or C₂-alkenyl, wherein the alkenyl may be optionallysubstituted with 1 to 2 substituents independently selected from C₁-C₂alkyl and fluoro.

Even more preferably R₅ is hydrogen, fluoro or methyl.

Most preferably R₅ is hydrogen.

Even more preferably R₆ is hydrogen, fluoro, methyl, C₁-C₃ alkoxy orC₁-C₂ haloalkoxy; or R₅ and R₆ together with the carbon atom to whichthey are attached represent C₂-alkenyl, wherein the alkenyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom methyl and fluoro.

More preferably still R₆ is hydrogen, methyl or C₁-C₃ alkoxy.

Most preferably R₆ is hydrogen.

Preferably R₇ is hydrogen, —C(═O)C₁-C₄ alkyl, —CH(═NOR_(r)),—C(═NOR_(c))C₁-C₄ alkyl, C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkenyl,C₃-C₅ cycloalkenyl or C₂-C₄ alkynyl, wherein the alkyl, cycloalkyl,alkenyl, alkynyl, cycloalkenyl may be optionally substituted with 1 to 2substituents independently selected from cyano, hydroxyl C₁-C₃ alkyl,C₁-C₃ alkoxy, fluoro and chloro or 1 to 3 substituents independentlyselected from fluoro and chloro.

More preferably R₇ is hydrogen, —CH(═NOR_(c)), —C(═NOR_(c))C₁-C₂ alkyl,C₁-C₄ alkyl, C₃-C₄ cycloalkyl, C₂-C₃ alkenyl or C₂-C₄ alkynyl, whereinthe alkyl, cycloalkyl, alkenyl and alkynyl may be optionally substitutedwith 1 to 2 substituents independently selected from cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy, chloro and fluoro or 1 to 3 fluoro substituents.

Even more preferably R₇ is hydrogen, —C(═NOR_(c))C₁-C₂ alkyl, C₁-C₄alkyl, cyclopropyl, C₂-C₃ alkenyl or C₂-C₃ alkynyl, wherein the alkyl,cyclopropyl, alkenyl and alkynyl may be optionally substituted with 1 to2 substituents independently selected from cyano, methyl, C₁-C₂ alkoxy,chloro and fluoro or 1 to 3 fluoro substituents.

More preferably still R₇ is hydrogen, C₁-C₄ alkyl, cyclopropyl or C₂-C₃alkenyl, wherein the alkyl, cyclopropyl, and alkenyl may be optionallysubstituted with 1 to 2 substituents independently selected from methyl,methoxy, chloro and fluoro or 1 to 3 fluoro substituents.

Yet more preferably R₇ is C₁-C₄ alkyl, cyclopropyl or C₂-C₃ alkenyl,wherein the alkyl, cyclopropyl, and alkenyl may be optionallysubstituted with 1 to 2 substituents independently selected from methyl,methoxy, chloro and fluoro or 1 to 3 fluoro substituents.

Most preferably R₇ is —C(Cl)═CH₂, —C(CH₃)═CH₂, isopropyl,1-methylcyclopropyl, trifluoromethyl, 1-fluorocyclopropyl, —CF₂CH₃,—CF(CH₃)CH₃ or tert-butyl.

Preferably R₈ and R₉ are each independently selected from hydrogen,halogen and C₁-C₄ alkyl; or R₈ and R₉ together with the carbon atom towhich they are attached represent C═O, or C₃-C₅ cycloalkyl, wherein thecycloalkyl may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro andchloro or 1 to 3 substituents independently selected from fluoro andchloro.

More preferably R₈ and R₉ are each independently selected from hydrogen,fluoro and C₁-C₂ alkyl; or R₈ and R₉ together with the carbon atom towhich they are attached represent C₃-C₄ cycloalkyl, wherein thecycloalkyl may be optionally substituted with 1 to 2 substituentsindependently selected from C₁-C₂ alkyl, fluoro and chloro.

Even more preferably R₈ is hydrogen or fluoro.

Most preferably R₈ is hydrogen.

Even more preferably R₉ is hydrogen, fluoro or methyl.

More preferably still R₉ is hydrogen or fluoro.

Most preferably R₉ is hydrogen.

Preferably each R₁₀ independently represents halogen, nitro, cyano,C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₅ cycloalkyl, C₁-C₄alkoxy, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy or C₁-C₄ alkylthio, whereinthe alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxyand alkylthio may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro andchloro or 1 to 3 substituents independently selected from fluoro andchloro; n is 0, 1, 2, 3 or 4.

More preferably each R₁₀ independently represents fluoro, chloro, bromo,C₁-C₃ alkyl, C₃-C₅ cycloalkyl, C₁-C₂ alkoxy or C₁-C₂ alkylthio, whereinthe alkyl, cycloalkyl, alkoxy and alkylthio may be optionallysubstituted with 1 to 2 substituents independently selected from C₁-C₂alkyl, C₁-C₂ alkoxy and fluoro or 1 to 3 fluoro substituents; n is 0, 1,2 or 3.

Even more preferably each R₁₀ independently represents fluoro, chloro,C₁-C₂ alkyl, cyclopropyl, or C₁-C₂ alkoxy, wherein the alkyl,cyclopropyl and alkoxy may be optionally substituted with 1 to 2substituents independently selected from methyl, methoxy and fluoro or 1to 3 fluoro substituents; n is 0, 1 or 2.

More preferably still each R₁₀ independently represents fluoro, chloroor C₁-C₂ alkyl, wherein the alkyl may be optionally substituted with 1methoxy substituents or 1 to 3 fluoro substituents; n is 0, 1 or 2.

Most preferably R₁₀ is fluoro; n is 0 or 1.

Preferably R₁₁ is hydrogen, fluoro, chloro or methyl.

More preferably R₁₁ is hydrogen, fluoro or chloro.

Most preferably R₁₁ is hydrogen or fluoro.

Preferably R₁₂ and R₁₃ are each independently selected from hydrogen,fluoro, chloro or methyl.

More preferably R₁₂ and R₁₃ are each independently hydrogen or fluoro.

Most preferably R₁₂ and R₁₃ are both hydrogen.

Preferably R₁₄ is hydrogen, C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₃-C₄alkenyl, C₃-C₄ alkynyl or C₁-C₄ alkoxy, wherein the alkyl, cycloalkyl,alkenyl, alkynyl and alkoxy may be optionally substituted with 1 to 3substituents independently selected from halogen, C₁-C₃ alkoxy and C₁-C₃alkylthio.

More preferably R₁₄ is hydrogen, methyl, ethyl, C₃-C₄ cycloalkyl, C₃-C₄alkenyl, C₃-C₄ alkynyl or C₁-C₃ alkoxy, wherein the alkyl, cycloalkyl,alkenyl, alkynyl and alkoxy may be optionally substituted with 1 to 3fluoro substituents or a C₁-C₂ alkoxy.

Even more preferably R₁₄ is hydrogen, methyl, ethyl, cyclopropyl, allyl,propargyl or methoxy, wherein the methyl and ethyl may be optionallysubstituted with 1 to 3 fluoro substituents or a methoxy.

Most preferably R₁₄ is hydrogen.

Preferably each R_(c) is independently selected from hydrogen, C₁-C₂alkyl, C₂-C₃ alkenyl, C₃-C₄ alkynyl and C₃-C₄ cycloalkyl(C₁-C₂)alkyl,wherein the alkyl, cycloalkyl, alkenyl and alkynyl groups may beoptionally substituted with 1 to 3 substituents independently selectedfrom fluoro and chloro.

More preferably each R_(c) is independently selected from hydrogen,C₁-C₂ alkyl, C₂-C₃ alkenyl, C₃-C₄ alkynyl, wherein the alkyl, alkenyland alkynyl groups may be optionally substituted with 1 to 3 fluorosubstituents.

Most preferably each R_(c) is independently selected from hydrogen andC₁-C₂ alkyl, wherein the alkyl group may be optionally substituted with1 to 3 fluoro substituents.

Embodiments according to the invention are provided as set out below.

Embodiment 1 provides compounds of formula (I), or a salt, enantiomer orN-oxide thereof, as defined above.

Embodiment 2 provides compounds according to embodiment 1, or a salt,enantiomer or N-oxide thereof, wherein R₁ is hydrogen, halogen, methylor cyano.

Embodiment 3 provides compounds according to embodiment 1 or 2, or asalt, enantiomer or N-oxide thereof, wherein R₂ and R₃ are eachindependently hydrogen, halogen or methyl.

Embodiment 4 provides compounds according to any one of embodiments 1, 2or 3, or a salt, enantiomer or N-oxide thereof, wherein R₄ is hydrogen,halogen, cyano, C₁-C₄ alkoxy or C₁-C₄ alkyl, wherein the alkoxy andalkyl may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro andchloro or 1 to 3 substituents independently selected from fluoro andchloro.

Embodiment 5 provides compounds according to any one of embodiments 1,2, 3 or 4, or a salt, enantiomer or N-oxide thereof, wherein R₅ and R₆are each independently selected from hydrogen, halogen, C₁-C₃ alkyl,C₁-C₃ alkoxy, C₁-C₃ haloalkoxy and C₁-C₃ alkylthio; or R₅ and R₆together with the carbon atom to which they are attached represent C═O,C═NOR_(c) or C₂-alkenyl, wherein the alkenyl may be optionallysubstituted with 1 or 2 substituents independently selected from cyano,C₁-C₃ alkyl, fluoro and chloro.

Embodiment 6 provides compounds according to any one of embodiments 1,2, 3, 4, or 5, or a salt, enantiomer or N-oxide thereof, wherein R₇ ishydrogen, C(═O)C₁-C₄ alkyl, —CH(═NOR_(c)), —C(═NOR_(c))C₁-C₄ alkyl,C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkenyl, C₃-C₅ cycloalkenyl orC₂-C₄ alkynyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl,cycloalkenyl may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, hydroxyl C₁-C₃ alkyl, C₁-C₃ alkoxy,fluoro and chloro or 1 to 3 substituents independently selected fromfluoro and chloro.

Embodiment 7 provides compounds according to any one of embodiments 1,2, 3, 4, 5, or 6, or a salt, enantiomer or N-oxide thereof, wherein R₈and R₉ are each independently selected from hydrogen, halogen and C₁-C₄alkyl; or R₈ and R₉ together with the carbon atom to which they areattached represent C═O, or C₃-C₅ cycloalkyl, wherein the cycloalkyl maybe optionally substituted with 1 to 2 substituents independentlyselected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro and chloro or 1to 3 substituents independently selected from fluoro and chloro.

Embodiment 8 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, or 7, or a salt, enantiomer or N-oxide thereof, whereineach R₁₀ independently represents halogen, nitro, cyano, C₁-C₄ alkyl,C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₅ cycloalkyl, C₁-C₄ alkoxy, C₃-C₄alkenyloxy, C₃-C₄ alkynyloxy or C₁-C₄ alkylthio, wherein the alkyl,cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy andalkylthio may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro andchloro or 1 to 3 substituents independently selected from fluoro andchloro; n is 0, 1, 2, 3 or 4.

Embodiment 9 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, or 8, or a salt, enantiomer or N-oxide thereof,wherein each R_(c) is independently selected from hydrogen, C₁-C₂ alkyl,C₂-C₃ alkenyl, C₃-C₄ alkynyl and C₃-C₄ cycloalkyl(C₁-C₂)alkyl, whereinthe alkyl, cycloalkyl, alkenyl and alkynyl groups may be optionallysubstituted with 1 to 3 substituents independently selected from fluoroand chloro.

Embodiment 10 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, or 9, or a salt, enantiomer or N-oxide thereof,wherein R₁₁ is hydrogen, fluoro, chloro or methyl.

Embodiment 11 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9 or 10, or a salt, enantiomer or N-oxide thereof,wherein R₁₂ and R₁₃ are each independently selected from hydrogen,fluoro, chloro or methyl.

Embodiment 12 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, or a salt, enantiomer or N-oxidethereof, wherein R₁ is hydrogen, fluoro, chloro or methyl.

Embodiment 13 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a salt, enantiomer or N-oxidethereof, wherein R₂ and R₃ are each independently hydrogen, fluoro,chloro or methyl.

Embodiment 14 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, or a salt, enantiomer orN-oxide thereof, wherein R₄ is hydrogen, fluoro, C₁-C₃ alkoxy or C₁-C₃alkyl, wherein the alkoxy and alkyl may be optionally substituted with 1to 2 substituents independently selected from cyano, C₁-C₂ alkoxy,fluoro and chloro or 1 to 3 substituents independently selected fromfluoro and chloro.

Embodiment 15 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a salt, enantiomer orN-oxide thereof, wherein R₅ and R₆ are each independently selected fromhydrogen, fluoro, chloro, C₁-C₂ alkyl, C₁-C₃ alkoxy and C₁-C₂haloalkoxy; or R₅ and R₆ together with the carbon atom to which they areattached represent C═NOR_(c) or C₂-alkenyl, wherein the alkenyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom C₁-C₂ alkyl and fluoro.

Embodiment 16 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, or a salt, enantiomeror N-oxide thereof, wherein R₇ is hydrogen, —CH(═NOR_(c)),—C(═NOR_(c))C₁-C₂ alkyl, C₁-C₄ alkyl, C₃-C₄ cycloalkyl, C₂-C₃ alkenyl orC₂-C₄ alkynyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, chloro and fluoro or 1 to 3fluoro substituents.

Embodiment 17 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, or a salt,enantiomer or N-oxide thereof, wherein R₈ and R₉ are each independentlyselected from hydrogen, fluoro and C₁-C₂ alkyl; or R₈ and R₉ togetherwith the carbon atom to which they are attached represent C₃-C₄cycloalkyl, wherein the cycloalkyl may be optionally substituted with 1to 2 substituents independently selected from C₁-C₂ alkyl, fluoro andchloro.

Embodiment 18 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, or a salt,enantiomer or N-oxide thereof, wherein each R₁₀ independently representsfluoro, chloro, bromo, C₁-C₃ alkyl, C₃-C₅ cycloalkyl, C₁-C₂ alkoxy orC₁-C₂ alkylthio, wherein the alkyl, cycloalkyl, alkoxy and alkylthio maybe optionally substituted with 1 to 2 substituents independentlyselected from C₁-C₂ alkyl, C₁-C₂ alkoxy and fluoro or 1 to 3 fluorosubstituents; n is 0, 1, 2 or 3.

Embodiment 19 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17 or 18, or a salt,enantiomer or N-oxide thereof, wherein each R_(c) is independentlyselected from hydrogen, C₁-C₂ alkyl, C₂-C₃ alkenyl, C₃-C₄ alkynyl,wherein the alkyl, alkenyl and alkynyl groups may be optionallysubstituted with 1 to 3 fluoro substituents.

Embodiment 20 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18 or 19, or asalt, enantiomer or N-oxide thereof, wherein R₁₁ is hydrogen, fluoro orchloro.

Embodiment 21 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20, ora salt, enantiomer or N-oxide thereof, wherein R₁₂ and R₁₃ are eachindependently hydrogen or fluoro.

Embodiment 22 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 or21, or a salt, enantiomer or N-oxide thereof, wherein R₁ is hydrogen,fluoro or methyl.

Embodiment 23 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21or 22, or a salt, enantiomer or N-oxide thereof, wherein R₂ and R₃ areeach independently hydrogen, fluoro or methyl.

Embodiment 24 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22 or 23, or a salt, enantiomer or N-oxide thereof, wherein R₄ ishydrogen, fluoro, C₁-C₃ alkoxy or C₁-C₂ alkyl, wherein the alkoxy andalkyl may be optionally substituted with 1 to 2 substituentsindependently selected from C₁-C₂ alkoxy, and fluoro or 1 to 3 fluorosubstituents.

Embodiment 25 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23 or 24, or a salt, enantiomer or N-oxide thereof, wherein R₅ ishydrogen, fluoro or methyl; and R₆ is hydrogen, fluoro, methyl, C₁-C₃alkoxy or C₁-C₂ haloalkoxy; or R₅ and R₆ together with the carbon atomto which they are attached represent C₂-alkenyl, wherein the alkenyl maybe optionally substituted with 1 to 2 substituents independentlyselected from methyl and fluoro.

Embodiment 26 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24 or 25, or a salt, enantiomer or N-oxide thereof, wherein R₇is hydrogen, —C(═NOR_(c))C₁-C₂ alkyl, C₁-C₄ alkyl, cyclopropyl, C₂-C₃alkenyl or C₂-C₃ alkynyl, wherein the alkyl, cyclopropyl, alkenyl andalkynyl may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, methyl, C₁-C₂ alkoxy, chloro andfluoro or 1 to 3 fluoro substituents.

Embodiment 27 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25 or 26, or a salt, enantiomer or N-oxide thereof, whereinR₈ is hydrogen or fluoro.

Embodiment 28 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26 or 27, or a salt, enantiomer or N-oxide thereof,wherein R₉ is hydrogen, fluoro or methyl.

Embodiment 29 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27 or 28, or a salt, enantiomer or N-oxide thereof,wherein each R₁₀ independently represents fluoro, chloro, C₁-C₂ alkyl,cyclopropyl, or C₁-C₂ alkoxy, wherein the alkyl, cyclopropyl and alkoxymay be optionally substituted with 1 to 2 substituents independentlyselected from methyl, methoxy and fluoro or 1 to 3 fluoro substituents;n is 0, 1 or 2.

Embodiment 30 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28 or 29, or a salt, enantiomer or N-oxidethereof, wherein each R_(c) is independently selected from hydrogen andC₁-C₂ alkyl, wherein the alkyl group may be optionally substituted with1 to 3 fluoro substituents.

Embodiment 31 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29 or 30, or a salt, enantiomer or N-oxidethereof, wherein R₁₁ is hydrogen or fluoro.

Embodiment 32 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30 or 31, or a salt, enantiomer orN-oxide thereof, wherein R₁₂ and R₁₃ are both hydrogen.

Embodiment 33 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31 or 32, or a salt, enantiomer orN-oxide thereof, wherein X is O.

Embodiment 34 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32 or 33, or a salt, enantiomeror N-oxide thereof, wherein R₁ is hydrogen or fluoro.

Embodiment 35 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33 or 34, or a salt,enantiomer or N-oxide thereof, wherein R₂ is hydrogen and R₃ is methyl;or R₂ is methyl and R₃ is hydrogen; or R₂ and R₃ are both hydrogen.

Embodiment 36 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34 or 35, or a salt,enantiomer or N-oxide thereof, wherein R₄ is hydrogen or C₁-C₂ alkyl,wherein the alkyl may be optionally substituted with 1 methoxysubstituent or 1 to 3 fluoro substituents.

Embodiment 37 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35 or 36, or a salt,enantiomer or N-oxide thereof, wherein R₅ is hydrogen.

Embodiment 38 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36 or 37, or asalt, enantiomer or N-oxide thereof, wherein R₆ is hydrogen, methyl orC₁-C₃ alkoxy.

Embodiment 39 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37 or 38, ora salt, enantiomer or N-oxide thereof, wherein R₇ is hydrogen, C₁-C₄alkyl, cyclopropyl or C₂-C₃ alkenyl, wherein the alkyl, cyclopropyl, andalkenyl may be optionally substituted with 1 to 2 substituentsindependently selected from methyl, methoxy, chloro and fluoro or 1 to 3fluoro substituents.

Embodiment 40 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38 or39, or a salt, enantiomer or N-oxide thereof, wherein R₈ is hydrogen orfluoro.

Embodiment 41 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39or 40, or a salt, enantiomer or N-oxide thereof, wherein R₉ is hydrogenor fluoro.

Embodiment 42 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40 or 41, or a salt, enantiomer or N-oxide thereof, wherein each R₁₀independently represents fluoro, chloro or C₁-C₂ alkyl, wherein thealkyl may be optionally substituted with 1 methoxy substituents or 1 to3 fluoro substituents; n is 0, 1 or 2.

Embodiment 43 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41 or 42, or a salt, enantiomer or N-oxide thereof, wherein R₁₄ ishydrogen, C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl orC₁-C₄ alkoxy, wherein the alkyl, cycloalkyl, alkenyl, alkynyl and alkoxymay be optionally substituted with 1 to 3 substituents independentlyselected from halogen, C₁-C₃ alkoxy and C₁-C₃ alkylthio.

Embodiment 44 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41 or 42, or a salt, enantiomer or N-oxide thereof, wherein R₁₄ ishydrogen, methyl, ethyl, C₃-C₄ cycloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynylor C₁-C₃ alkoxy, wherein the alkyl, cycloalkyl, alkenyl, alkynyl andalkoxy may be optionally substituted with 1 to 3 fluoro substituents ora C₁-C₂ alkoxy.

Embodiment 45 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41 or 42, or a salt, enantiomer or N-oxide thereof, wherein R₁₄ ishydrogen, methyl, ethyl, cyclopropyl, allyl, propargyl or methoxy,wherein the methyl and ethyl may be optionally substituted with 1 to 3fluoro substituents or a methoxy.

Embodiment 46 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41 or 42, or a salt, enantiomer or N-oxide thereof, wherein R₁₄ ishydrogen.

Embodiment 47 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45 or 46, or a salt, enantiomer or N-oxide thereof,wherein R₁ is fluoro.

Embodiment 48 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46 or 47, or a salt, enantiomer or N-oxidethereof, wherein R₄ is methyl.

Embodiment 49 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47 or 48, or a salt, enantiomer or N-oxidethereof, wherein R₆ is hydrogen.

Embodiment 50 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47, 48 or 49, or a salt, enantiomer orN-oxide thereof, wherein R₇ is C₁-C₄ alkyl, cyclopropyl or C₂-C₃alkenyl, wherein the alkyl, cyclopropyl, and alkenyl may be optionallysubstituted with 1 to 2 substituents independently selected from methyl,methoxy, chloro and fluoro or 1 to 3 fluoro substituents.

Embodiment 51 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47, 48, 49 or 50, or a salt, enantiomer orN-oxide thereof, wherein R₈ is hydrogen.

Embodiment 52 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50 or 51, or a salt, enantiomeror N-oxide thereof, wherein R₉ is hydrogen.

Embodiment 53 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51 or 52, or a salt,enantiomer or N-oxide thereof, wherein R₁₀ is fluoro; n is 0 or 1.

Embodiment 54 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21,22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39,40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52 or 53, or a salt,enantiomer or N-oxide thereof, wherein R₇ is —C(Cl)═CH₂, —C(CH₃)═CH₂,isopropyl, 1-methylcyclopropyl, trifluoromethyl, 1-fluorocyclopropyl,—CF₂CH₃, —CF(CH₃)CH₃ or tert-butyl.

One group of compounds according to the invention are those of formula(I′):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, nand R_(c) are as defined for compounds of formula (I), or a salt,enantiomer or N-oxide thereof. Preferred definitions of R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, n and R_(c) are as definedfor compounds of formula (I).

One group of compounds according to the invention are those of formula(I″):

wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, nand R_(c) are as defined for compounds of formula (I), or a salt,enantiomer or N-oxide thereof. Preferred definitions of R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄, n and R_(c) are as definedfor compounds of formula (I).

A preferred group of compounds according to the invention are those offormula (I-1) which are compounds of formula (I) wherein X is O or S; R₁is hydrogen, halogen, methyl or cyano; R₂ and R₃ are each independentlyhydrogen, halogen or methyl; R₄ is hydrogen, halogen, cyano, C₁-C₄alkoxy or C₁-C₄ alkyl, wherein the alkoxy and alkyl may be optionallysubstituted with 1 to 2 substituents independently selected from cyano,C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro and chloro or 1 to 3 substituentsindependently selected from fluoro and chloro; R₅ and R₆ are eachindependently selected from hydrogen, halogen, C₁-C₃ alkyl, C₁-C₃alkoxy, C₁-C₃ haloalkoxy and C₁-C₃ alkylthio; or R₅ and R₆ together withthe carbon atom to which they are attached represent C═O, C═NOR_(c) orC₂-alkenyl, wherein the alkenyl may be optionally substituted with 1 or2 substituents independently selected from cyano, C₁-C₃ alkyl, fluoroand chloro; R₇ is hydrogen, C(═O)C₁-C₄ alkyl, —CH(═NOR_(c)),—C(═NOR_(c))C₁-C₄ alkyl, C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkenyl,C₃-C₅ cycloalkenyl or C₂-C₄ alkynyl, wherein the alkyl, cycloalkyl,alkenyl, alkynyl, cycloalkenyl may be optionally substituted with 1 to 2substituents independently selected from cyano, hydroxyl C₁-C₃ alkyl,C₁-C₃ alkoxy, fluoro and chloro or 1 to 3 substituents independentlyselected from fluoro and chloro; R₈ and R₉ are each independentlyselected from hydrogen, halogen and C₁-C₄ alkyl; or R₈ and R₉ togetherwith the carbon atom to which they are attached represent C═O, or C₃-C₅cycloalkyl, wherein the cycloalkyl may be optionally substituted with 1to 2 substituents independently selected from cyano, C₁-C₃ alkyl, C₁-C₃alkoxy, fluoro and chloro or 1 to 3 substituents independently selectedfrom fluoro and chloro; each R₁₀ independently represents halogen,nitro, cyano, C₁-C₄ alkyl, C₂-C₄ alkenyl, C₂-C₄ alkynyl, C₃-C₅cycloalkyl, C₁-C₄ alkoxy, C₃-C₄ alkenyloxy, C₃-C₄ alkynyloxy or C₁-C₄alkylthio, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy,alkenyloxy, alkynyloxy and alkylthio may be optionally substituted with1 to 2 substituents independently selected from cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy, fluoro and chloro or 1 to 3 substituents independentlyselected from fluoro and chloro; n is 0, 1, 2, 3 or 4; each R_(c) isindependently selected from hydrogen, C₁-C₂ alkyl, C₂-C₃ alkenyl, C₃-C₄alkynyl and C₃-C₄ cycloalkyl(C₁-C₂)alkyl, wherein the alkyl, cycloalkyl,alkenyl and alkynyl groups may be optionally substituted with 1 to 3substituents independently selected from fluoro and chloro; R₁₁ ishydrogen, fluoro, chloro or methyl; R₁₂ and R₁₃ are each independentlyselected from hydrogen, fluoro, chloro or methyl; and R₁₄ is hydrogen,C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynyl or C₁-C₄alkoxy, wherein the alkyl, cycloalkyl, alkenyl, alkynyl and alkoxy maybe optionally substituted with 1 to 3 substituents independentlyselected from halogen, C₁-C₃ alkoxy and C₁-C₃ alkylthio; or a salt,enantiomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-1a) which are compounds of formula (I-1) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-1b) which are compounds of formula (I-1) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-2) which are compounds of formula (I) wherein X is Oor S; R₁ is hydrogen, fluoro, chloro or methyl; R₂ and R₃ are eachindependently hydrogen, fluoro, chloro or methyl; R₄ is hydrogen,fluoro, C₁-C₃ alkoxy or C₁-C₃ alkyl, wherein the alkoxy and alkyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom cyano, C₁-C₂ alkoxy, fluoro and chloro or 1 to 3 substituentsindependently selected from fluoro and chloro; R₅ and R₆ are eachindependently selected from hydrogen, fluoro, chloro, C₁-C₂ alkyl, C₁-C₃alkoxy and C₁-C₂ haloalkoxy; or R₅ and R₆ together with the carbon atomto which they are attached represent C═NOR_(c) or C₂-alkenyl, whereinthe alkenyl may be optionally substituted with 1 to 2 substituentsindependently selected from C₁-C₂ alkyl and fluoro; R₇ is hydrogen,—CH(═NOR_(c)), —C(═NOR_(c))C₁-C₂ alkyl, C₁-C₄ alkyl, C₃-C₄ cycloalkyl,C₂-C₃ alkenyl or C₂-C₄ alkynyl, wherein the alkyl, cycloalkyl, alkenyland alkynyl may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, chloro andfluoro or 1 to 3 fluoro substituents; R₈ and R₉ are each independentlyselected from hydrogen, fluoro and C₁-C₂ alkyl; or R₈ and R₉ togetherwith the carbon atom to which they are attached represent C₃-C₄cycloalkyl, wherein the cycloalkyl may be optionally substituted with 1to 2 substituents independently selected from C₁-C₂ alkyl, fluoro andchloro; each R₁₀ independently represents fluoro, chloro, bromo, C₁-C₃alkyl, C₃-C₅ cycloalkyl, C₁-C₂ alkoxy or C₁-C₂ alkylthio, wherein thealkyl, cycloalkyl, alkoxy and alkylthio may be optionally substitutedwith 1 to 2 substituents independently selected from C₁-C₂ alkyl, C₁-C₂alkoxy and fluoro or 1 to 3 fluoro substituents; n is 0, 1, 2 or 3; eachR_(c) is independently selected from hydrogen, C₁-C₂ alkyl, C₂-C₃alkenyl, C₃-C₄ alkynyl, wherein the alkyl, alkenyl and alkynyl groupsmay be optionally substituted with 1 to 3 fluoro substituents; R₁₁ ishydrogen, fluoro or chloro; R₁₂ and R₁₃ are each independently hydrogenor fluoro; and R₁₄ is hydrogen, methyl, ethyl, C₃-C₄ cycloalkyl, C₃-C₄alkenyl, C₃-C₄ alkynyl or C₁-C₃ alkoxy, wherein the alkyl, cycloalkyl,alkenyl, alkynyl and alkoxy may be optionally substituted with 1 to 3fluoro substituents or a C₁-C₂ alkoxy; or a salt, enantiomer or N-oxidethereof.

One group of compounds according to this embodiment are compounds offormula (I-2a) which are compounds of formula (I-2) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-2b) which are compounds of formula (I-2) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-3) which are compounds of formula (I) wherein X is Oor S; R₁ is hydrogen, fluoro or methyl; R₂ and R₃ are each independentlyhydrogen, fluoro or methyl; R₄ is hydrogen, fluoro, C₁-C₃ alkoxy orC₁-C₂ alkyl, wherein the alkoxy and alkyl may be optionally substitutedwith 1 to 2 substituents independently selected from C₁-C₂ alkoxy, andfluoro or 1 to 3 fluoro substituents; R₅ is hydrogen, fluoro or methyl;R₆ is hydrogen, fluoro, methyl, C₁-C₃ alkoxy or C₁-C₂ haloalkoxy; or R₅and R₆ together with the carbon atom to which they are attachedrepresent C₂-alkenyl, wherein the alkenyl may be optionally substitutedwith 1 to 2 substituents independently selected from methyl and fluoro;R₇ is hydrogen, —C(═NOR_(c))C₁-C₂ alkyl, C₁-C₄ alkyl, cyclopropyl, C₂-C₃alkenyl or C₂-C₃ alkynyl, wherein the alkyl, cyclopropyl, alkenyl andalkynyl may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, methyl, C₁-C₂ alkoxy, chloro andfluoro or 1 to 3 fluoro substituents; R₈ is hydrogen or fluoro; R₉ ishydrogen, fluoro or methyl; each R₁₀ independently represents fluoro,chloro, C₁-C₂ alkyl, cyclopropyl, or C₁-C₂ alkoxy, wherein the alkyl,cyclopropyl and alkoxy may be optionally substituted with 1 to 2substituents independently selected from methyl, methoxy and fluoro or 1to 3 fluoro substituents; n is 0, 1 or 2; each R_(c) is independentlyselected from hydrogen and C₁-C₂ alkyl, wherein the alkyl group may beoptionally substituted with 1 to 3 fluoro substituents; R₁₁ is hydrogenor fluoro; R₁₂ and R₁₃ are both hydrogen; and R₁₄ is hydrogen, methyl,ethyl, cyclopropyl, allyl, propargyl or methoxy, wherein the methyl andethyl may be optionally substituted with 1 to 3 fluoro substituents or amethoxy; or a salt, enantiomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-3a) which are compounds of formula (I-3) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-3b) which are compounds of formula (I-3) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-4) which are compounds of formula (I) wherein X is Oor S; R₁ is hydrogen or fluoro; R₂ is hydrogen and R₃ is methyl; or R₂is methyl and R₃ is hydrogen; or R₂ and R₃ are both hydrogen; R₄ ishydrogen or C₁-C₂ alkyl, wherein the alkyl may be optionally substitutedwith 1 methoxy substituent or 1 to 3 fluoro substituents; R₅ ishydrogen; R₆ is hydrogen, methyl or C₁-C₃ alkoxy; R₇ is hydrogen, C₁-C₄alkyl, cyclopropyl or C₂-C₃ alkenyl, wherein the alkyl, cyclopropyl, andalkenyl may be optionally substituted with 1 to 2 substituentsindependently selected from methyl, methoxy, chloro and fluoro or 1 to 3fluoro substituents; R₈ is hydrogen or fluoro; R₉ is hydrogen or fluoro;each R₁₀ independently represents fluoro, chloro or C₁-C₂ alkyl, whereinthe alkyl may be optionally substituted with 1 methoxy substituents or 1to 3 fluoro substituents; n is 0, 1 or 2; R₁₁ is hydrogen or fluoro; andR₁₂, R₁₃ and R₁₄ are all hydrogen; or a salt, enantiomer or N-oxidethereof.

One group of compounds according to this embodiment are compounds offormula (I-4a) which are compounds of formula (I-4) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-4b) which are compounds of formula (I-4) wherein X is S.

A further preferred group of compounds according to the invention arethose of formula (I-5) which are compounds of formula (I) wherein X is Oor S; R₁ is fluoro; R₂ is hydrogen and R₃ is methyl; or R₂ is methyl andR₃ is hydrogen; or R₂ and R₃ are both hydrogen; R₄ is methyl; R₅ ishydrogen; R₆ is hydrogen; R₇ is —C(Cl)═CH₂, —C(CH₃)═CH₂, isopropyl,1-methylcyclopropyl, trifluoromethyl, 1-fluorocyclopropyl, —CF₂CH₃,—CF(CH₃)CH₃ or tert-butyl; R₈ is hydrogen; R₉ is hydrogen; R₁₀ isfluoro; n is 0 or 1; R₁ is hydrogen or fluoro; and R₁₂, R₁₃ and R₁₄ areall hydrogen; or a salt, enantiomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-5a) which are compounds of formula (I-5) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-5b) which are compounds of formula (I-5) wherein X is S.

Compounds according to the invention may possess any number of benefitsincluding, inter alia, advantageous levels of biological activity forprotecting plants against diseases that are caused by fungi or superiorproperties for use as agrochemical active ingredients (for example,greater biological activity, an advantageous spectrum of activity, anincreased safety profile, improved physico-chemical properties, orincreased biodegradability).

Specific examples of compounds of formula (I) are illustrated in theTables A1 to A15 below: Table A1 provides 274 compounds of formula (I-x)

wherein R₁, R₂ and R₃ are all H and R₁₁, R₁₂, R₁₃, R₁₄ are all Hand wherein the values of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ and n (if R₁₀and n are present) are as defined in Table Z below:

TABLE Z Entry R₄ R₅ R₆ R₇ R₈ R₉ R₁₀ 1 H H H CH₃ H H — 2 H H H CH₂CH₃ H H— 3 H H H CH₂CH₂CH₃ H H — 4 H H H CH₂CF₃ H H — 5 H H H CH(CH₃)₂ H H — 6H H H CH═CH₂ H H — 7 H H H C(CH₃)═CH₂ H H — 8 H H H C(Cl)═CH₂ H H — 9 HH H C(CH₃)═CF₂ H H — 10 H H H C(F)═CH₂ H H — 11 H H H C(CH₃)₃ H H — 12 HH H CF(CH₃)₂ H H — 13 H H H C(OCH₃)(CH₃)₂ H H — 14 H H H C(OH)(CH₃)₂ H H— 15 H H H C(CN)(CH₃)₂ H H — 16 H H H C(SCH₃)(CH₃)₂ H H — 17 H H HCH₂OCH₃ H H — 18 H H H CF₃ H H — 19 H H H CHF₂ H H — 20 H H H CF₂CH₃ H H— 21 H H H CF₂Cl H H — 22 H H H CH═CF₂ H H — 23 H H H CH═C(CH₃)H H H —24 H H H CH═C(CH₃)₂ H H — 25 H H H C≡C(CH₃) H H — 26 H H HC≡C(cyclopropyl) H H — 27 H H H C≡C(CF₃) H H — 28 H H H cyclopropyl H H— 29 H H H 1-methylcyclopropyl H H — 30 H H H 1-fluorocyclopropyl H H —31 H H H 1-cyanocyclopropyl H H — 32 H H H 1-Methylthiocyclopropyl H H —33 H H H cyclobutyl H H — 34 H H H 1-fluorocyclobutyl H H — 35 H H H3,3-difluorocyclobutyl H H — 36 H H H CH═O H H — 37 H H H C(CH₃)═O H H —38 H H H C(CF₃)═O H H — 39 H H H CH═NOCH₃ H H — 40 H H H C(CH₃)═NOCH₃ HH — 41 H H H C(CF₃)═NOCH₃ H H — 42 CH₃ H H CH₃ H H — 43 CH H H CH₂CH3 HH — 44 CH H H CH₂CH₂CH₃ H H — 45 CH₃ H H CH₂CF₃ H H — 46 CH₃ H HCH(CH₃)₂ H H — 47 CH₃ H H CH═CH₂ H H — 48 CH₃ H H C(CH₃)═CH₂ H H — 49CH₃ H H C(Cl)═CH₂ H H — 50 CH₃ H H C(CH₃)═CF₂ H H — 51 CH₃ H H C(F)═CH₂H H — 52 CH₃ H H C(CH₃)₃ H H — 53 CH H H CF(CH₃)₂ H H — 54 CH H HC(OCH₃)(CH₃)₂ H H — 55 CH H H C(OH)(CH₃)₂ H H — 56 CH₃ H H C(CN)(CH₃)₂ HH — 57 CH H H C(SCH₃)(CH₃)₂ H H — 58 CH₃ H H CH₂OCH₃ H H — 59 CH H H CF₃H H — 60 CH₃ H H CHF₂ H H — 61 CH₃ H H CF₂CH₃ H H — 62 CH₃ H H CF₂Cl H H— 63 CH₃ H H CH═CF₂ H H — 64 CH₃ H H CH═C(CH₃)H H H — 65 CH₃ H HCH═C(CH₃)₂ H H — 66 CH₃ H H C≡C(CH₃) H H — 67 CH₃ H H C≡C(cyclopropyl) HH — 68 CH₃ H H C≡C(CF₃) H H — 69 CH₃ H H cyclopropyl H H — 70 CH₃ H H1-methylcyclopropyl H H — 71 CH₃ H H 1-fluorocyclopropyl H H — 72 CH₃ HH 1-cyanocyclopropyl H H — 73 CH H H 1-Methylthiocyclopropyl H H — 74 CHH H cyclobutyl H H — 75 CH H H 1-fluorocyclobutyl H H — 76 CH₃ H H3,3-difluorocyclobutyl H H — 77 CH H H CH═O H H — 78 CH₃ H H C(CH₃)═O HH — 79 CH H H C(CF₃)═O H H — 80 CH₃ H H CH═NOCH₃ H H — 81 CH₃ H HC(CH₃)═NOCH₃ H H — 82 CH₃ H H C(CF₃)═NOCH₃ H H — 83 H CH₃ H CH₃ H H — 84H CH₃ CH₃ CH₃ H H — 85 H cyclopropyl CH₃ H H — 86 H CH₃ CH₃ CH₂CH₃ H H —87 H cyclopropyl CH₂CH₃ H H — 88 CH₂CH₃ H H CH₃ H H — 89 CH₂CH₃ H HCH₂CH₃ H H — 90 CH₂CH₃ H H CH₂CF₃ H H — 91 CH₂CH₃ H H CH(CH₃)₂ H H — 92CH₂CH₃ H H CH═CH₂ H H — 93 CH₂CH₃ H H C(CH₃)═CH₂ H H — 94 CH₂CH₃ H HC(CH₃)₃ H H — 95 CH₂CH₃ H H CF(CH₃)₂ H H — 96 CH₂CH₃ H H C(CN)(CH₃)₂ H H— 97 CH₂CH₃ H H C(OCH₃)(CH₃)₂ H H — 98 CH₂CH₃ H H CH₂OCH₃ H H — 99CH₂CH₃ H H CF₃ H H — 100 CH₂CH₃ H H CHF₂ H H — 101 CH₂CH₃ H H CF₂CH₃ H H— 102 CH₂CH₃ H H C≡C(CH₃) H H — 103 CH₂CH₃ H H C≡C(cyclopropyl) H H —104 CH₂CH₃ H H cyclopropyl H H — 105 CH₂CH₃ H H 1-methylcyclopropyl H H— 106 CH₂CH₃ H H 1-fluorocyclopropyl H H — 107 CH₂CH₃ H H1-cyanocyclopropyl H H — 108 CH₂CH₃ H H 1-Methylthiocyclopropyl H H —109 CH₂CH₃ H H cyclobutyl H H — 110 CH₂CH₃ H H 1-fluorocyclobutyl H H —111 CH₂CH₃ H H 3,3-difluorocyclobutyl H H — 112 CH₂CH₃ H H C(CH₃)═O H H— 113 CH₂CH₃ H H C(CF₃)═O H H — 114 CH₂CH₃ H H C(CH₃)═NOCH₃ H H — 115CH₂CH₃ H H C(CF₃)═NOCH₃ H H — 116 CN H H CH₃ H H — 117 CN H H CH₂CH₃ H H— 118 CN H H CH₂CF₃ H H — 119 CN H H CH(CH₃)₂ H H — 120 CN H H C(CH₃)₃ HH — 121 CN H H CF(CH₃)₂ H H — 122 CN H H CF₃ H H — 123 CH₂OCH₃ H H CH₃ HH — 124 CH₂OCH₃ H H CH₂CH₃ H H — 125 CH₂OCH₃ H H CH₂CF₃ H H — 126CH₂OCH₃ H H CH(CH₃)₂ H H — 127 CH₂OCH₃ H H CH═CH₂ H H — 128 CH₂OCH₃ H HC(CH₃)═CH₂ H H — 129 CH₂OCH₃ H H C(CH₃)3 H H — 130 CH₂OCH₃ H H CF(CH₃)₂H H — 131 CH₂OCH₃ H H CF₃ H H — 132 CH₂OCH₃ H H CHF₂ H H — 133 CH₂OCH₃ HH CF₂CH₃ H H — 134 CH₂OCH₃ H H CF₂Cl H H — 135 CH₂OCH₃ H H CH═CF₂ H H —136 CH₂OCH₃ H H cyclopropyl H H — 137 CH₂OCH₃ H H 1-methylcyclopropyl HH — 138 CH₂OCH₃ H H 1-fluorocyclopropyl H H — 139 CH₂OCH₃ H H1-cyanocyclopropyl H H — 140 F H H H H H — 141 F H H CH₃ H H — 142 F H HCH₂CH₃ H H — 143 F H H CH₂CF₃ H H — 144 F H H CH(CH₃)₂ H H — 145 F H HCH═CH₂ H H — 146 F H H C(CH₃)═CH₂ H H — 147 F H H C(CH₃)₃ H H — 148 F HH CF(CH₃)₂ H H — 149 F H H C(OCH₃)(CH₃)₂ H H — 150 F H H CH₂OCH₃ H H —151 F H H CF₃ H H — 152 F H H CHF₂ H H — 153 F H H CF₂CH₃ H H — 154 F HH CF₂Cl H H — 155 F H H CH═CF₂ H H — 156 F H H CH═C(CH₃)H H H — 157 F HH CH═C(CH₃)₂ H H — 158 F H H C≡C(CH₃) H H — 159 F H H C≡C(cyclopropyl) HH — 160 F H H cyclopropyl H H — 161 F H H 1-methylcyclopropyl H H — 162F H H 1-fluorocyclopropyl H H — 163 F H H 1-cyanocyclopropyl H H — 164 FH H cyclobutyl H H — 165 F H H 1-fluorocyclobutyl H H — 166 F H H3,3-difluorocyclobutyl H H — 167 F H H CH═O H H — 168 F H H C(CH₃)═O H H— 169 F H H C(CF₃)═O H H — 170 F H H CH═NOCH₃ H H — 171 F H HC(CH₃)═NOCH₃ H H — 172 F H H C(CF₃)═NOCH₃ H H — 173 OCH₃ H H H H H — 174OCH₃ H H CH₃ H H — 175 OCH₃ H H CH₂CH₃ H H — 176 OCH₃ H H CH₂CF₃ H H —177 OCH₃ H H CH(CH₃)₂ H H — 178 OCH₃ H H CH═CH₂ H H — 179 OCH₃ H HC(CH₃)═CH₂ H H — 180 OCH₃ H H C(CH₃)₃ H H — 181 OCH₃ H H CF(CH₃)₂ H H —182 OCH₃ H H C(OCH₃)(CH₃)₂ H H — 183 OCH₃ H H CH₂OCH₃ H H — 184 OCH₃ H HCF₃ H H — 185 OCH₃ H H CHF₂ H H — 186 OCH₃ H H CF₂CH₃ H H — 187 OCH₃ H HCF₂Cl H H — 188 OCH₃ H H CH═CF₂ H H — 189 OCH₃ H H CH═C(CH₃)H H H — 190OCH₃ H H CH═C(CH₃)₂ H H — 191 OCH₃ H H C≡C(CH₃) H H — 192 OCH₃ H HC≡C(cyclopropyl) H H — 193 OCH₃ H H cyclopropyl H H — 194 OCH₃ H H1-methylcyclopropyl H H — 195 OCH₃ H H 1-fluorocyclopropyl H H — 196OCH₃ H H 1-cyanocyclopropyl H H — 197 OCH₃ H H cyclobutyl H H — 198 OCH₃H H 1-fluorocyclobutyl H H — 199 OCH₃ H H 3,3-difluorocyclobutyl H H —200 OCH₃ H H CH═O H H — 201 OCH₃ H H C(CH₃)═O H H — 202 OCH₃ H HC(CF₃)═O H H — 203 OCH₃ H H CH═NOCH₃ H H — 204 OCH₃ H H C(CH₃)═NOCH₃ H H— 205 OCH₃ H H C(CF₃)═NOCH₃ H H — 206 OCF₃ H H H H H — 207 OCF₃ H H CH₃H H — 208 OCF₃ H H CH₂CH₃ H H — 209 OCF₃ H H CH₂CF₃ H H — 210 OCF₃ H HCH(CH₃)₂ H H — 211 OCF₃ H H CH═CH₂ H H — 212 OCF₃ H H C(CH₃)═CH₂ H H —213 OCF₃ H H C(CH₃)₃ H H — 214 OCF₃ H H CF(CH₃)₂ H H — 215 OCF₃ H HC(OCH₃)(CH₃)₂ H H — 216 OCF₃ H H CH₂OCH₃ H H — 217 OCF₃ H H CF₃ H H —218 OCF₃ H H CHF₂ H H — 219 OCF₃ H H CF₂CH₃ H H — 220 OCF₃ H H CF₂Cl H H— 221 OCF₃ H H CH═CF₂ H H — 222 OCF₃ H H CH═C(CH₃)H H H — 223 OCF₃ H HCH═C(CH₃)₂ H H — 224 OCF₃ H H C≡C(CH₃) H H — 225 OCF₃ H HC≡C(cyclopropyl) H H — 226 OCF₃ H H cyclopropyl H H — 227 OCF₃ H H1-methylcyclopropyl H H — 228 OCF₃ H H 1-fluorocyclopropyl H H — 229OCF₃ H H 1-cyanocyclopropyl H H — 230 OCF₃ H H cyclobutyl H H — 231 OCF₃H H 1-fluorocyclobutyl H H — 232 OCF₃ H H 3,3-difluorocyclobutyl H H —233 OCF₃ H H CH═O H H — 234 OCF₃ H H C(CH₃)═O H H — 235 OCF₃ H HC(CF₃)═O H H — 236 OCF₃ H H CH═NOCH₃ H H — 237 OCF₃ H H C(CH₃)═NOCH₃ H H— 238 OCF₃ H H C(CF₃)═NOCH₃ H H — 239 OCH(CH₃)₂ H H H H H — 240OCF(CH₃)₂ H H H H H — 241 OCH(CH₃)₂ H H CH₃ H H — 242 OCH(CH₃)₂ H H CF₃H H — 243 CH₃ OCF₃ H H H H — 244 CH₃ OCHF₂ H H H H — 245 CH₃ OCH₂F H H HH — 246 CH₃ SCF₃ H H H H — 247 CH₃ SCHF₂ H H H H — 248 CH₃ SCH₂F H H H H— 249 CH₃ H H CF₃ F F — 250 CH₃ F F CF₃ H H — 251 CH₃ CH₃ H CF₃ H H —252 CH₃ H H CF₃ CH₃ H — 253 CH₃ H H CH(CH₃)₂ F F — 254 CH₃ F F CH(CH₃)₂H H 255 CH₃ CH₃ H CH(CH₃)₂ H H 256 CH₃ H H CH(CH₃)₂ CH₃ H 257 CH₃ H HCF₃ H H 2-F 258 CH₃ H H CF₃ H H 3-F 259 CH₃ H H CF₃ H H 4-F 260 CH₃ H HCF₃ H H 2-Cl 261 CH₃ H H CF₃ H H 3-Cl 262 CH₃ H H CF₃ H H 4-Cl 263 CH₃ HH CF₃ H H 2-CH₃ 264 CH₃ H H CF₃ H H 3-CH₃ 265 CH₃ H H CF₃ H H 4-CH₃ 266CH₃ H H CH(CH₃)₂ H H 2-F 267 CH₃ H H CH(CH₃)₂ H H 3-F 268 CH₃ H HCH(CH₃)₂ H H 4-F 269 CH₃ H H CH(CH₃)₂ H H 2-Cl 270 CH₃ H H CH(CH₃)₂ H H3-Cl 271 CH₃ H H CH(CH₃)₂ H H 4-Cl 272 CH₃ H H CH(CH₃)₂ H H 2-CH₃ 273CH₃ H H CH(CH₃)₂ H H 3-CH₃ 274 CH₃ H H CH(CH₃)₂ H H 4-CH₃Table A2 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H, R₁ is fluoro, R₂ and R₃ are H and wherein the values ofR₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.Table A3 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H, R₁ is chloro, R₂ and R₃ are H and wherein the values ofR₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.Table A4 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H, R₁ is methyl, R₂ and R₃ are H and wherein the values ofR₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.Table A5 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H, R₁ is cyano, R₂ and R₃ are H and wherein the values ofR₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.Table A6 provides 274 compounds of formula (I-x) wherein R is fluoro,R₁₂, R₁₃, R₁₄ are all H, R₁ is H, R₂ and R₃ are H and wherein the valuesof R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.Table A7 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H are all H, R₂ is methyl, R₁ and R₃ are H and wherein thevalues of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Zabove.Table A8 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H are all H, R₃ is methyl, R₁ and R₂ are H and wherein thevalues of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Zabove.Table A9 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H are all H, R₂ is methyl, R₁ is fluoro and R₃ is H andwherein the values of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined inTable Z above.Table A10 provides 274 compounds of formula (I-x) wherein R₁₁, R₁₂, R₁₃,R₁₄ are all H, R₃ is methyl, R₁ is fluoro and R₂ is H and wherein thevalues of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Zabove.Table A11 provides 274 compounds of formula (I-x) wherein R₁₂, R₁₃, R₁₄are H, R₂ and R₃ are H, R₁ and R₁₁ are fluoro, and wherein the values ofR₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.Table A12 provides 274 compounds of formula (I-x) wherein R₁₂, R₁₃, R₁₄are H, R₂ is H, R₃ is methyl, R₁ and R₁₁ are fluoro, and wherein thevalues of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Zabove.Table A13 provides 274 compounds of formula (I-x) wherein R₁₂, R₁₃, R₁₄are H, R₃ is H, R₂ is methyl, R₁ and R₁₁ are fluoro, and wherein thevalues of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Zabove.Table A14 provides 274 compounds of formula (I-y)

wherein R₁₁, R₁₂, R₁₃, R₁₄, R₁, R₂ and R₃ are all H and wherein thevalues of R₄, R₅, R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Zabove.Table A15 provides 248 compounds of formula (I-y) wherein R₁ is fluoro,R₁₁, R₁₂, R₁₃, R₁₄, R₂ and R₃ are H and wherein the values of R₄, R₅,R₆, R₇, R₈, R₉ and R₁₀ are as defined in Table Z above.

Compounds of the present invention can be made as shown in the followingschemes, in which, unless otherwise stated, the definition of eachvariable is as defined above for a compound of formula (I).

Among the various reported methods for preparing compounds of formula(I-a), wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃,R₁₄ and n are as defined for compounds of formula (I), the most widelyapplied involve treatment of carboxylic acid (III), wherein R₄, R₅, R₆,R₇, R₈, R₉, R₁₀ and n are as defined for compounds of formula (I), withan activating agent like phosgene, thionyl chloride or oxalyl chlorideor an amide coupling reagent like dicyclohexylcarbodiimide in an inertorganic solvent like tetrahydrofuran (THF) or dimethylformamide (DMF)and reaction with an amine of formula (II), wherein R₁, R₂, R₃, R₁₁,R₁₂, R₁₃ and R₁₄ are as defined for compounds of formula (I), in thepresence of a catalyst like dimethylaminopyridine as described in Chem.Soc. Rev., 2009, 606-631 or Tetrahedron 2005, 10827-10852. This is shownin Scheme 1.

Alternatively, compounds of formula (I-a), wherein R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and n are as defined forcompounds of formula (I), can be obtained from a compound of formula(I-aa) wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃and n are as defined for compounds of formula (I) and R₁₄ is H, upontreatment with a base such as sodium hydride, potassium or cesiumcarbonate, and an alkylating agent such as alkyl-, alkenyl- or alkynylhalide (preferably iodide, bromide, chloride) in an inert organicsolvent like tetrahydrofuran (THF), acetone or dimethylformamide (DMF).This is shown in scheme 2.

Compounds of formula (I-aa), wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₀, R₁₁, R₁₂, R₁₃ and n are as defined for compounds of formula (I) andR₁₄ is H, can be prepared by the reaction of compounds of formula (II),wherein R₁, R₂, R₃, R₁₁, R₁₂ and R₁₃ are as defined for compounds offormula (I), and an ester of formula (IV) wherein R₄, R₅, R₆, R₇, R₈,R₉, R₁₀ and n are as defined for compounds of formula (I) and R₂₀ isC₁-C₆ alkyl, with a Lewis acid such as trimethyl aluminium in an inertorganic solvent like tetrahydrofuran (THF) or dimethylformamide (DMF)under heating. This is shown in Scheme 3.

Alternatively, compounds of formula (I-a), wherein R₁, R₂, R₃, R₄, R₅,R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and n are as defined forcompounds of formula (I), can be prepared by the coupling of compound(V), wherein R₁, R₂, R₃, R₁₁, R₁₂ and R₁₃ are as defined for compoundsof formula (I) and Hal is halogen, preferably chloro, bromo or iodo, andcompound (VI), wherein R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₄ and n are asdefined for compounds of formula (I), in the presence of a base such ascesium carbonate or sodium tertiary-butoxide in the presence of atransition metal catalyst such as a copper-based catalyst such as copperoxide, copper (I) acetylacetonate or copper (I)bromide-1,10-phenanthroline complex, a nickel catalyst such asDichloro(1,3-bis(diphenylphosphino)propane)nickel or a palladium-basedcatalyst such asChloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(III),X-Phos aminobiphenyl palladium chloride precatalyst or[1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II)dichloride in an aprotic solvent such as toluene orN,N-dimethylformamide at room temperature or while heating. This isshown in Scheme 4.

Compounds of formula (II), wherein R₁, R₂, R₃, R₁₁, R₁₂, R₁₃ and R₁₄ areas defined for compounds of formula (I) and (III-a) wherein R₁₄ is H,can be prepared by the coupling of compound (V), wherein R₁, R₂, R₃,R₁₁, R₁₂ and R₁₃ are as defined for compounds of formula (I) and Hal ishalogen, preferably chloro, bromo or iodo, and a primary amine R₁₄NH₂(VII-a) or ammonia or an ammonium salt (like ammonium hydroxide orammonium acetate), in the presence of a base such as potassiumphosphate, cesium carbinate or sodium tertiary-butoxide in the presenceof a copper-based catalyst such as copper (I) acetylacetonate, copperoxide or copper (I) iodide in the presence of a ligand such as1,10-phenanthroline or L-proline. Alternatively the reaction can beperformed in the presence of a palladium or nickel based transitionmetal catalyst such aschloro(2-dicyclohexylphosphino-2′,4′,6′-triisopropyl-1,1′-biphenyl)[2-(2′-amino-1,1′-biphenyl)]palladium(II),X-Phos aminobiphenyl palladium chloride precatalyst or[1,3-Bis(2,6-Diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride or Nickel dicyclooctadiene in combination withJosiphos SL-J003-1 as ligand. The reaction can be carried out in variousaprotic solvent such as toluene, dioxane or N,N-dimethylformamide atroom temperature or while heating. For instance the preparation of (II)when R₁₄ is cyclopropyl has been described in Organic Letters 2016,18(6), 1442-1445. This is shown in Scheme 5.

Alternatively compounds of formula (II-a) wherein R₁, R₂, R₃, R₁₁, R₁₂and R₁₃ are as defined for compounds of formula (I), can be prepared bythe coupling of compound (V), wherein R₁, R₂, R₃, R₁₁, R₁₂ and R₁₃ areas defined for compounds of formula (I) and Hal is halogen, preferablychloro, bromo or iodo, and a primary amine R₃₀NH₂ (VII) where R₃₀ is aprotecting group such as benzyl or alkylcarbonyl, under transition metalcatalysed conditions such as those described in Scheme 4, followed bydeprotection of the the group R₃₀, under various conditions such thosedescribed in Greene's Protective Groups in Organic Synthesis (Peter G.M. Wuts, Theodora W. Greene, John Wiley & Sons Ed.) Compounds of formula(V), wherein R₁, R₂, R₃, R₁₁, R₁₂ and R₁₃ are as defined for compoundsof formula (I) and Hal is halogen, preferably chloro, bromo or iodo canbe prepared by treatment of compounds of formula (VIII) wherein R₁, R₂,R₃, R₁₁, R₁₂ and R₁₃ with a halogenating agent like N-iodosuccinimide,bromine or chlorine in an inert solvent such as acetonitrile or aceticacid at room temperature or while heating as described in WO 2005113539or JP 2001322979. Alternatively, compounds of formula (V), wherein R₁,R₂, R₃, R₁₁, R₁₂ and R₁₃ are as defined for compounds of formula (I) andHal is halogen, preferably chloro, bromo or iodo, can be prepared bytreatment of propargylated anilines of formula (IX), wherein R₁, R₂, R₃,R₁₁, R₁₂ and R₁₃ are as defined for compounds of formula (I), with ahalogenating agent like iodine or bromine in an inert solvent likeacetonitrile and a base like sodium hydrogen carbonate at temperaturesbetween 0° C. and 80° C. as described in Org. Lett. 2005, 763-766. Thisis shown in Scheme 6.

Compounds of formula (VIII), R₁, R₂, R₃, R₁₁, R₁₂ and R₁₃ are as definedfor compounds of formula (I), can be prepared by using various synthesistechniques known to the person skilled in the art as described in RSCAdv. 2014, 4, 24463 or March's Advanced Organic Chemistry, Smith andMarch, 6^(th) edition, Wiley, 2007.

Alternatively, compounds of formula (II-a) wherein R₁, R₂, R₃, R₁₁, R₁₂and R₁₃ are as defined for compounds of formula (I) can be also preparedfrom carboxylic acids of formula (X) through an intermediary isocyanateof formula (XI) which can be hydrolyzed with aqueous acid or base attemperatures between 0° C. and 100° C. as shown in scheme 7.

Among the various protocols reported for the transformation of acid (X)to isocyanate (XI), the following have found wide spread application:

1) Treatment of acid (X) with diphenylphosphoryl azide and an amine baselike tributylamine in an inert organic solvent like toluene attemperatures between 50° C. and 120° C. to give isocyanate (XI) asdescribed in Aust. J. Chem., 1973, 1591-3.

2) Treatment of acid (X) with an activating agent like thionyl chlorideor propylphosphonic anhydride in the presence of an azide source likesodium azide and an amine base like triethyl amine in an inert solventlike THF at temperatures between 20° C. and 100° C. as described inSynthesis 2011, 1477-1483.

3) Conversion of acid (X) to the corresponding hydroxamic acids whichcan then be treated with a dehydrating agent like para-toluenesulfonylchloride and a base like triethylamine in an inert organic solvent liketoluene at temperatures between 20° C. and 120° C.

4) Conversion of acid (X) to the corresponding primary carboxamide whichcan then be treated with an oxidizing agent such as diacetoxyiodobenzeneand an acid such as trifluoroacetic acid or para-toluenesulfonic acid ina solvent like acetonitrile at temperatures between 0° C. and 100° C. asdescribed in J. Org. Chem. 1984, 4212-4216.

5) Conversion of acid (X) to the corresponding primary carboxamide whichcan then be treated with an oxidizing agent such as bromine and a basesuch as sodium hydroxide in a solvent like water or methanol attemperatures between 0° C. and 100° C.

Carboxylic acids of formula (X) wherein R₁, R₂, R₃, R₁₁, R₁₂ and R₁₃ areas defined for compounds of formula (I) can be prepared by variousmethods as shown in Scheme 8 and many are commercially available.

Among the many reported methods for their preparation, the followinghave been widely applied:

1) Transformation of anilines of formula (XII) to quinolones of formula(XIV) by reaction with a malonate derivative of formula (XIII) in aninert solvent like diphenyl ether at temperatures between 100° C. and260° C. as described in US 20070015758, followed by well-knownfunctional group interconversion which is generally known to a personskilled in the art and also described in WO 2007133637.

2) Transformation of compounds of formula (V) to organometallicintermediates by lithium-halogen exchange with an alkyl lithium reagentlike s-butyl lithium or magnesium-halogen exchange with tri n-butylmagnesate in an ethereal solvent like THF at temperatures between −90°C. and +20° C. and subsequent reaction with CO₂.

3) Transformation of compounds of formula (V) in the presence of acarbon monoxide source, a base like triethylamine, water or anequivalent thereof and a suitably ligated transition metal catalystcontaining for example palladium as described in J. Am. Chem. Soc. 2013,2891-2894 (and references therein) or Tetrahedron 2003, 8629-8640.

4) Hydrolysis of a compound of formula (XV) under basic or acidicaqueous conditions. As shown in scheme 7, compounds of formula (XV) canbe prepared from compounds of formula (V) by treatment with a cyanidesource like zinc cyanide in the presence of a palladium, nickel orcopper catalyst in an inert solvent like DMF at temperatures between 20°C. and 150° C. as described in J. Org. Chem. 2011, 665-668 or Bull.Chem. Soc. Jpn. 1993, 2776-8.

Among the various reported methods for preparing compounds of formula(VI), wherein R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₄ and n are as defined forcompounds of formula (I), the most widely applied involve treatment ofcarboxylic acid (III), wherein R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and n are asdefined for compounds of formula (I), with an activating agent likephosgene, thionyl chloride or oxalyl chloride or an amide couplingreagent like dicyclohexylcarbodiimide in an inert organic solvent liketetrahydrofuran (THF) or dimethylformamide (DMF) and reaction with anamine R₁₄NH₂ (VII-a) or ammonia or an ammonium salt such as ammoniumchloride or ammonium hydroxide in the presence or absence of a catalystlike dimethylaminopyridine as described in Chem. Soc. Rev., 2009,606-631 or Tetrahedron 2005, 10827-10852. This is shown in Scheme 9.

A person skilled in the art will appreciate that carboxylic acids offormula (III) wherein R₄, R₅, R₆, R₇, R₈, R₉, R₁₀ and n are as definedfor compounds of formula (I) can be prepared from the correspondingesters, for instance from compounds of formula (IV) wherein R₄, R₅, R₆,R₇, R₈, R₉, R₁₀ and n are as defined for compounds of formula (I) andR₂₀ is C₁-C₆ alkyl. Similarly a person skilled in the art willappreciate that the alpha position of these esters can be functionalizedby deprotonation with a strong base like lithium diisopropylamine in aninert solvent like THF at temperatures between −78° C. and 20° C.followed by reaction with an electrophilic reagent like an alkyl iodideor a source of electrophilic fluorine, as described in March's AdvancedOrganic Chemistry, Smith and March, 6^(th) edition, Wiley, 2007. Thisreaction can be repeated to prepare acids of formula (III) fromcommercially available esters.

As shown in scheme 10, compounds of general formula (I-b), whereinwherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ andn are as defined for compounds of formula (I), can be prepared fromcompounds of general formula (I-a), wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇,R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and n are as defined for compounds offormula (I), by treatment with a deoxothionating agent like P₄S₁₀ orLawesson reagent in an inert organic solvent like toluene attemperatures between 20° C. and 150° C.

Alternatively, the compounds of formula (I-a), wherein R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and n are as defined forcompounds of formula (I), can be obtained by transformation of acompound of formula (I-c), wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, R₉,R₁₁, R₁₂, R₁₃, R₁₄ and n are as defined for formula (I) and wherein Yrepresents chlorine, bromine or iodine in a solvent, in the presence ofor absence of a base, and in the presence of a coupling reagent and ametal catalyst. There are no particular limitations on the couplingagent, catalyst, solvent and bases, provided it is used in ordinarycoupling reactions, such as those described in “Cross-CouplingReactions: A Practical Guide (Topics in Current Chemistry)”, edited byNorio Miyaura und S. L. Buchwald (editions Springer), or“Metal-Catalyzed Cross-Coupling Reactions”, edited by Armin de Meijereand Frangois Diederich (editions WILEY-VCH). This is shown in Scheme 11.

Alternatively, the compounds of formula (I-a) wherein R₁, R₂, R₃, R₄,R₅, R₆, R₇, R₈, R₉, R₁₀, R₁₁, R₁₂, R₁₃, R₁₄ and n are as defined forcompounds of formula (I), can be obtained by transformation of another,closely related, compound of formula (I-a) using standard synthesistechniques known to the person skilled in the art. Non-exhaustiveexamples include oxidation reactions, reduction reactions, hydrolysisreactions, coupling reactions, aromatic nucleophilic or electrophilicsubstitution reactions, nucleophilic substitution reactions,nucleophilic addition reactions, olefination reactions, oxime formation,alkylation and halogenation reactions.

Certain intermediates described in the above schemes are novel and assuch form a further aspect of the invention.

The compounds of formula (I) can be used in the agricultural sector andrelated fields of use e.g. as active ingredients for controlling plantpests or on non-living materials for control of spoilage microorganismsor organisms potentially harmful to man. The novel compounds aredistinguished by excellent activity at low rates of application, bybeing well tolerated by plants and by being environmentally safe. Theyhave very useful curative, preventive and systemic properties and may beused for protecting numerous cultivated plants. The compounds of formula(I) can be used to inhibit or destroy the pests that occur on plants orparts of plants (fruit, blossoms, leaves, stems, tubers, roots) ofdifferent crops of useful plants, while at the same time protecting alsothose parts of the plants that grow later e.g. from phytopathogenicmicroorganisms.

It is also possible to use compounds of formula (I) as fungicide. Theterm “fungicide” as used herein means a compound that controls,modifies, or prevents the growth of fungi. The term “fungicidallyeffective amount” means the quantity of such a compound or combinationof such compounds that is capable of producing an effect on the growthof fungi. Controlling or modifying effects include all deviation fromnatural development, such as killing, retardation and the like, andprevention includes barrier or other defensive formation in or on aplant to prevent fungal infection.

It is also possible to use compounds of formula (I) as dressing agentsfor the treatment of plant propagation material, e.g., seed, such asfruits, tubers or grains, or plant cuttings (for example rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil. The propagation material can be treatedwith a composition comprising a compound of formula (I) before planting:seed, for example, can be dressed before being sown. The compounds offormula (I) can also be applied to grains (coating), either byimpregnating the seeds in a liquid formulation or by coating them with asolid formulation. The composition can also be applied to the plantingsite when the propagation material is being planted, for example, to theseed furrow during sowing. The invention relates also to such methods oftreating plant propagation material and to the plant propagationmaterial so treated.

Furthermore the compounds according to present invention can be used forcontrolling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products,in food storage, in hygiene management.

In addition, the invention could be used to protect non-living materialsfrom fungal attack, e.g. lumber, wall boards and paint.

Compounds of formula (I) and fungicidal compositions containing them maybe used to control plant diseases caused by a broad spectrum of fungalplant pathogens. They are effective in controlling a broad spectrum ofplant diseases, such as foliar pathogens of ornamental, turf, vegetable,field, cereal, and fruit crops.

These fungi and fungal vectors of disease, as well as phytopathogenicbacteria and viruses, which may be controlled are for example:

Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp,Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A.niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomycesdermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp.including B. dothidea, B. obtusa, Botrytis spp. including B. cinerea,Candida spp. including C. albicans, C. glabrata, C. krusei, C.lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans,Ceratocystis spp, Cercospora spp. including C. arachidicola,Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,

Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C.musae,

Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechslera spp,Elsinoe spp,

Epidermophyton spp, Erwinia amylovora, Erysiphe spp. including E.cichoracearum,

Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F.langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F.subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi,Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate,Guignardia bidwellii, Gymnosporangium juniperi-virginianae,Helminthosporium spp, Hemileia spp, Histoplasma spp. including H.capsulatum, Laetisaria fuciformis, Leptographium lindbergi, Leveillulataurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp,Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola,M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioidesspp, Penicillium spp. including P. digitatum, P. italicum, Petriellidiumspp, Peronosclerospora spp. Including P. maydis, P. philippinensis andP. sorghi, Peronospora spp, Phaeosphaeria nodorum, Phakopsorapachyrhizi, Phellinus igniarus, Phialophora spp, Phoma spp, Phomopsisviticola, Phytophthora spp. including P. infestans, Plasmopara spp.including P. halstedii, P. viticola, Pleospora spp., Podosphaera spp.including P. leucotricha, Polymyxa graminis, Polymyxa betae,Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonosporaspp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila,Puccinia Spp. including P. hordei, P. recondita, P. striiformis, P.triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. includingP. oryzae, Pythium spp. including P. ultimum, Ramularia spp, Rhizoctoniaspp, Rhizomucor pusillus, Rhizopus arrhizus, Rhynchosporium spp,Scedosporium spp. including S. apiospermum and S. prolificans,Schizothyrium pomi,

Sclerotinia spp, Sclerotium spp, Septoria spp, including S. nodorum, S.tritici, Sphaerotheca macularis, Sphaerotheca fusca (Sphaerothecafuliginea), Sporothorix spp, Stagonospora nodorum, Stemphylium spp.,Stereum hirsutum, Thanatephorus cucumeris, Thielaviopsis basicola,Tilletia spp, Trichoderma spp. including T. harzianum, T.pseudokoningii, T. viride,

Trichophyton spp, Typhula spp, Uncinula necator, Urocystis spp, Ustilagospp, Venturia spp. including V. inaequalis, Verticillium spp, andXanthomonas spp.

In particular, compounds of formula (I) and fungicidal compositionscontaining them may be used to control plant diseases caused by a broadspectrum of fungal plant pathogens in the Basidiomycete, Ascomycete,Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete,Glomeromycete and/or Mucoromycete classes.

These pathogens may include:

Oomycetes, including Phytophthora diseases such as those caused byPhytophthora capsici, Phytophthora infestans, Phytophthora sojae,Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi,Phytophthora citricola, Phytophthora citrophthora and Phytophthoraerythroseptica; Pythium diseases such as those caused by Pythiumaphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythiumirregulare and Pythium ultimum; diseases caused by Peronosporales suchas Peronospora destructor, Peronospora parasitica, Plasmopara viticola,Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida,Sclerophthora macrospora and Bremia lactucae; and others such asAphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghiand Sclerospora graminicola.

Ascomycetes, including blotch, spot, blast or blight diseases and/orrots for example those caused by Pleosporales such as Stemphyliumsolani, Stagonospora tainanensis, Spilocaea oleaginea, Setosphaeriaturcica, Pyrenochaeta lycoperisici, Pleospora herbarum, Phomadestructiva, Phaeosphaeria herpotrichoides, Phaeocryptocus gaeumannii,Ophiosphaerella graminicola, Ophiobolus graminis, Leptosphaeriamaculans, Hendersonia creberrima, Helminthosporium triticirepentis,Setosphaeria turcica, Drechslera glycines, Didymella bryoniae,Cycloconium oleagineum, Corynespora cassiicola, Cochliobolus sativus,Bipolaris cactivora, Venturia inaequalis, Pyrenophora teres, Pyrenophoratritici-repentis, Alternaria alternata, Alternaria brassicicola,Alternaria solani and Alternaria tomatophila, Capnodiales such asSeptoria tritici, Septoria nodorum, Septoria glycines, Cercosporaarachidicola, Cercospora sojina, Cercospora zeae-maydis, Cercosporellacapsellae and Cercosporella herpotrichoides, Cladosporium carpophilum,Cladosporium effusum, Passalora fulva, Cladosporium oxysporum,Dothistroma septosporum, Isariopsis clavispora, Mycosphaerellafijiensis, Mycosphaerella graminicola, Mycovellosiella koepkeii,Phaeoisariopsis bataticola, Pseudocercospora vitis, Pseudocercosporellaherpotrichoides, Ramularia beticola, Ramularia collo-cygni,Magnaporthales such as Gaeumannomyces graminis, Magnaporthe grisea,Pyricularia oryzae, Diaporthales such as Anisogramma anomala,Apiognomonia errabunda, Cytospora platani, Diaporthe phaseolorum,Discula destructiva, Gnomonia fructicola, Greeneria uvicola, Melanconiumjuglandinum, Phomopsis viticola, Sirococcusclavigignenti-juglandacearum, Tubakia dryina, Dicarpella spp., Valsaceratosperma, and others such as Actinothyrium graminis, Ascochyta pisi,Aspergillus flavus, Aspergillus fumigatus, Aspergillus nidulans,Asperisporium caricae, Blumeriella jaapii, Candida spp., Capnodiumramosum, Cephaloascus spp., Cephalosporium gramineum, Ceratocystisparadoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus, Coccidioidesspp., Cylindrosporium padi, Diplocarpon malae, Drepanopeziza campestris,Elsinoe ampelina, Epicoccum nigrum, Epidermophyton spp., Eutypa lata,Geotrichum candidum, Gibellina cerealis, Gloeocercospora sorghi,Gloeodes pomigena, Gloeosporium perennans; Gloeotinia temulenta,Griphospaeria corticola, Kabatiella lini, Leptographium microsporum,Leptosphaerulinia crassiasca, Lophodermium seditiosum, Marssoninagraminicola, Microdochium nivale, Monilinia fructicola, Monographellaalbescens, Monosporascus cannonballus, Naemacyclus spp., Ophiostomanovo-ulmi, Paracoccidioides brasiliensis, Penicillium expansum,Pestalotia rhododendri, Petriellidium spp., Pezicula spp., Phialophoragregata, Phyllachora pomigena, Phymatotrichum omnivora, Physalosporaabdita, Plectosporium tabacinum, Polyscytalum pustulans, Pseudopezizamedicaginis, Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdoclinepseudotsugae, Rhynchosporium secalis, Sacrocladium oryzae, Scedosporiumspp., Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor;Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae,Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonemaphacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata,Thielviopsis basicola, Trichoseptoria fructigena, Zygophialajamaicensis; powdery mildew diseases for example those caused byErysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinulanecator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaeramacularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaeradiffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis;molds for example those caused by Botryosphaeriales such as Dothiorellaaromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea,Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodiatheobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllostictacucurbitacearum; anthracnoses for example those caused by Glommerelalessuch as Colletotrichum gloeosporioides, Colletotrichum lagenarium,Colletotrichum gossypii, Glomerella cingulata, and Colletotrichumgraminicola; and wilts or blights for example those caused byHypocreales such as Acremonium strictum, Claviceps purpurea, Fusariumculmorum, Fusarium graminearum, Fusarium virguliforme, Fusariumoxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense,Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladiumspp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride,Trichothecium roseum, and Verticillium theobromae.

Basidiomycetes, including smuts for example those caused byUstilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilagotritici, Ustilago zeae, rusts for example those caused by Puccinialessuch as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporiumipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata,Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei,Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,Pucciniastrum coryli, or Uredinales such as Cronartium ribicola,Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsorapachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzscheliadiscolor and Uromyces viciae-fabae; and other rots and diseases such asthose caused by Cryptococcus spp., Exobasidium vexans, Marasmiellusinoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis,Urocystis agropyri, Itersonilia perplexans, Corticium invisum,Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani,Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora,Neovossia moliniae and Tilletia caries.

Blastocladiomycetes, such as Physoderma maydis.

Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopusarrhizus,

As well as diseases caused by other species and genera closely relatedto those listed above.

In addition to their fungicidal activity, the compounds and compositionscomprising them may also have activity against bacteria such as Erwiniaamylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonassyringae, Strptomyces scabies and other related species as well ascertain protozoa.

Within the scope of present invention, target crops and/or useful plantsto be protected typically comprise perennial and annual crops, such asberry plants for example blackberries, blueberries, cranberries,raspberries and strawberries; cereals for example barley, maize (corn),millet, oats, rice, rye, sorghum triticale and wheat; fibre plants forexample cotton, flax, hemp, jute and sisal; field crops for examplesugar and fodder beet, coffee, hops, mustard, oilseed rape (canola),poppy, sugar cane, sunflower, tea and tobacco; fruit trees for exampleapple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pearand plum; grasses for example Bermuda grass, bluegrass, bentgrass,centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass;herbs such as basil, borage, chives, coriander, lavender, lovage, mint,oregano, parsley, rosemary, sage and thyme; legumes for example beans,lentils, peas and soya beans; nuts for example almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palms for exampleoil palm; ornamentals for example flowers, shrubs and trees; othertrees, for example cacao, coconut, olive and rubber; vegetables forexample asparagus, aubergine, broccoli, cabbage, carrot, cucumber,garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin,rhubarb, spinach and tomato; and vines for example grapes.

The useful plants and/or target crops in accordance with the inventioninclude conventional as well as genetically enhanced or engineeredvarieties such as, for example, insect resistant (e.g. Bt. and VIPvarieties) as well as disease resistant, herbicide tolerant (e.g.glyphosate- and glufosinate-resistant maize varieties commerciallyavailable under the trade names RoundupReady® and LibertyLink®) andnematode tolerant varieties. By way of example, suitable geneticallyenhanced or engineered crop varieties include the Stoneville 5599BRcotton and Stoneville 4892BR cotton varieties.

The term “useful plants” and/or “target crops” is to be understood asincluding also useful plants that have been rendered tolerant toherbicides like bromoxynil or classes of herbicides (such as, forexample, HPPD inhibitors, ALS inhibitors, for example primisulfuron,prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” and/or “target crops” is to be understood asincluding those which naturally are or have been rendered resistant toharmful insects. This includes plants transformed by the use ofrecombinant DNA techniques, for example, to be capable of synthesisingone or more selectively acting toxins, such as are known, for example,from toxin-producing bacteria. Examples of toxins which can be expressedinclude 6-endotoxins, vegetative insecticidal proteins (Vip),insecticidal proteins of bacteria colonising nematodes, and toxinsproduced by scorpions, arachnids, wasps and fungi. An example of a cropthat has been modified to express the Bacillus thuringiensis toxin isthe Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprisingmore than one gene that codes for insecticidal resistance and thusexpresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seedmaterial thereof can also be resistant to multiple types of pests(so-called stacked transgenic events when created by geneticmodification). For example, a plant can have the ability to express aninsecticidal protein while at the same time being herbicide tolerant,for example Herculex I® (Dow AgroSciences, Pioneer Hi-BredInternational).

The term “useful plants” and/or “target crops” is to be understood asincluding also useful plants which have been so transformed by the useof recombinant DNA techniques that they are capable of synthesisingantipathogenic substances having a selective action, such as, forexample, the so-called “pathogenesis-related proteins” (PRPs, see e.g.EP-A-0 392 225). Examples of such antipathogenic substances andtransgenic plants capable of synthesising such antipathogenic substancesare known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353191. The methods of producing such transgenic plants are generally knownto the person skilled in the art and are described, for example, in thepublications mentioned above.

Toxins that can be expressed by transgenic plants include, for example,insecticidal proteins from Bacillus cereus or Bacillus popilliae; orinsecticidal proteins from Bacillus thuringiensis, such as 6-endotoxins,e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, orvegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to beunderstood by 6-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1 Fa2,Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins(Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybridtoxins, truncated toxins and modified toxins. Hybrid toxins are producedrecombinantly by a new combination of different domains of thoseproteins (see, for example, WO 02/15701). Truncated toxins, for examplea truncated Cry1Ab, are known. In the case of modified toxins, one ormore amino acids of the naturally occurring toxin are replaced. In suchamino acid replacements, preferably non-naturally present proteaserecognition sequences are inserted into the toxin, such as, for example,in the case of Cry3A055, a cathepsin-G-recognition sequence is insertedinto a Cry3A toxin (see WO03/018810).

More examples of such toxins or transgenic plants capable ofsynthesising such toxins are disclosed, for example, in EP-A-0 374 753,WO93/07278, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cry1-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bbl toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1 Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard I1® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bbl toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603×MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue deTervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603×MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

The term “locus” as used herein means fields in or on which plants aregrowing, or where seeds of cultivated plants are sown, or where seedwill be placed into the soil. It includes soil, seeds, and seedlings, aswell as established vegetation.

The term “plants” refers to all physical parts of a plant, includingseeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, andfruits.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

Pesticidal agents referred to herein using their common name are known,for example, from “The Pesticide Manual”, 15th Ed., British CropProtection Council 2009.

The compounds of formula (I) may be used in unmodified form or,preferably, together with the adjuvants conventionally employed in theart of formulation. To this end they may be conveniently formulated inknown manner to emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions or suspensions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects.

Suitable carriers and adjuvants, e.g. for agricultural use, can be solidor liquid and are substances useful in formulation technology, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilizers. Suchcarriers are for example described in WO 97/33890.

Suspension concentrates are aqueous formulations in which finely dividedsolid particles of the active compound are suspended. Such formulationsinclude anti-settling agents and dispersing agents and may furtherinclude a wetting agent to enhance activity as well an anti-foam and acrystal growth inhibitor. In use, these concentrates are diluted inwater and normally applied as a spray to the area to be treated. Theamount of active ingredient may range from 0.5% to 95% of theconcentrate.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other liquid carriers. The particlescontain the active ingredient retained in a solid matrix. Typical solidmatrices include fuller's earth, kaolin clays, silicas and other readilywet organic or inorganic solids. Wettable powders normally contain from5% to 95% of the active ingredient plus a small amount of wetting,dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositionsdispersible in water or other liquid and may consist entirely of theactive compound with a liquid or solid emulsifying agent, or may alsocontain a liquid carrier, such as xylene, heavy aromatic naphthas,isophorone and other non-volatile organic solvents. In use, theseconcentrates are dispersed in water or other liquid and normally appliedas a spray to the area to be treated. The amount of active ingredientmay range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively coarseparticles and are usually applied without dilution to the area in whichtreatment is required. Typical carriers for granular formulationsinclude sand, fuller's earth, attapulgite clay, bentonite clays,montmorillonite clay, vermiculite, perlite, calcium carbonate, brick,pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corncobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate,sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide,titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth,calcium sulphate and other organic or inorganic materials which absorbor which can be coated with the active compound. Granular formulationsnormally contain 5% to 25% of active ingredients which may includesurface-active agents such as heavy aromatic naphthas, kerosene andother petroleum fractions, or vegetable oils; and/or stickers such asdextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finelydivided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the activeingredient enclosed in an inert porous shell which allows escape of theenclosed material to the surroundings at controlled rates. Encapsulateddroplets are typically 1 to 50 microns in diameter. The enclosed liquidtypically constitutes 50 to 95% of the weight of the capsule and mayinclude solvent in addition to the active compound. Encapsulatedgranules are generally porous granules with porous membranes sealing thegranule pore openings, retaining the active species in liquid forminside the granule pores. Granules typically range from 1 millimetre to1 centimetre and preferably 1 to 2 millimetres in diameter. Granules areformed by extrusion, agglomeration or prilling, or are naturallyoccurring. Examples of such materials are vermiculite, sintered clay,kaolin, attapulgite clay, sawdust and granular carbon. Shell or membranematerials include natural and synthetic rubbers, cellulosic materials,styrene-butadiene copolymers, polyacrylonitriles, polyacrylates,polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene and other organic solvents. Pressurisedsprayers, wherein the active ingredient is dispersed in finely-dividedform as a result of vaporisation of a low boiling dispersant solventcarrier, may also be used.

Suitable agricultural adjuvants and carriers that are useful informulating the compositions of the invention in the formulation typesdescribed above are well known to those skilled in the art.

Liquid carriers that can be employed include, for example, water,toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethylketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone,amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol,alkyl acetates, diacetonalcohol, 1,2-dichloropropane, diethanolamine,p-diethylbenzene, diethylene glycol, diethylene glycol abietate,diethylene glycol butyl ether, diethylene glycol ethyl ether, diethyleneglycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide,1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether,dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethylacetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-trichloroethane,2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycolbutyl ether, ethylene glycol methyl ether, gamma-butyrolactone,glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate,hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate,isooctane, isophorone, isopropyl benzene, isopropyl myristate, lacticacid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamylketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyloleate, methylene chloride, m-xylene, n-hexane, n-octylamine,octadecanoic acid, octyl amine acetate, oleic acid, oleylamine,o-xylene, phenol, polyethylene glycol (PEG400), propionic acid,propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene,triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin,mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, methanol, ethanol, isopropanol, and highermolecular weight alcohols such as amyl alcohol, tetrahydrofurfurylalcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol,glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrierof choice for the dilution of concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk,diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller'searth, cotton seed hulls, wheat flour, soybean flour, pumice, woodflour, walnut shell flour and lignin.

A broad range of surface-active agents are advantageously employed inboth said liquid and solid compositions, especially those designed to bediluted with carrier before application. These agents, when used,normally comprise from 0.1% to 15% by weight of the formulation. Theycan be anionic, cationic, non-ionic or polymeric in character and can beemployed as emulsifying agents, wetting agents, suspending agents or forother purposes. Typical surface active agents include salts of alkylsulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonatesalts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkyleneoxide addition products, such as nonylphenol-C.sub. 18 ethoxylate;alcohol-alkylene oxide addition products, such as tridecylalcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate;alkylnaphthalenesulfonate salts, such as sodiumdibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride; polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions includecrystallisation inhibitors, viscosity modifiers, suspending agents,spray droplet modifiers, pigments, antioxidants, foaming agents,anti-foaming agents, light-blocking agents, compatibilizing agents,antifoam agents, sequestering agents, neutralising agents and buffers,corrosion inhibitors, dyes, odorants, spreading agents, penetrationaids, micronutrients, emollients, lubricants and sticking agents.

In addition, further, other biocidally active ingredients orcompositions may be combined with the compositions of the invention andused in the methods of the invention and applied simultaneously orsequentially with the compositions of the invention. When appliedsimultaneously, these further active ingredients may be formulatedtogether with the compositions of the invention or mixed in, forexample, the spray tank. These further biocidally active ingredients maybe fungicides, herbicides, insecticides, bactericides, acaricides,nematicides and/or plant growth regulators.

In addition, the compositions of the invention may also be applied withone or more systemically acquired resistance inducers (“SAR” inducer).SAR inducers are known and described in, for example, U.S. Pat. No.6,919,298 and include, for example, salicylates and the commercial SARinducer acibenzolar-S-methyl.

The compounds of formula (I) are normally used in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession with further compounds. These furthercompounds can be e.g. fertilizers or micronutrient donors or otherpreparations, which influence the growth of plants. They can also beselective herbicides or non-selective herbicides as well asinsecticides, fungicides, bactericides, nematicides, molluscicides ormixtures of several of these preparations, if desired together withfurther carriers, surfactants or application promoting adjuvantscustomarily employed in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal)compositions for controlling or protecting against phytopathogenicmicroorganisms, comprising as active ingredient at least one compound offormula (I) or of at least one preferred individual compound asabove-defined, in free form or in agrochemically usable salt form, andat least one of the above-mentioned adjuvants.

The invention therefore provides a composition, preferably a fungicidalcomposition, comprising at least one compound formula (I) anagriculturally acceptable carrier and optionally an adjuvant. Anagricultural acceptable carrier is for example a carrier that issuitable for agricultural use. Agricultural carriers are well known inthe art. Preferably said composition may comprise at least one or morepesticidally active compounds, for example an additional fungicidalactive ingredient in addition to the compound of formula (I).

The compound of formula (I) may be the sole active ingredient of acomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may, in some cases, result in unexpected synergisticactivities.

Examples of suitable additional active ingredients include thefollowing: 1,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines,aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides,anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones,benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles,benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles,benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids,chloronitriles, cinnamic acid amides, copper containing compounds,cyanoacetamideoximes, cyanoacrylates, cyanoimidazoles,cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides,dicarboximides, dimethylsulphamates, dinitrophenol carbonates,dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiinocompounds, dithiocarbamates, dithioethers, dithiolanes,ethyl-amino-thiazole carboxamides, ethyl-phosphonates, furancarboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles,guanidines, herbicides/plant growth regulatosr, hexopyranosylantibiotics, hydroxy(2-amino)pyrimidines, hydroxyanilides,hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growthregulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines,maleimides, mandelic acid amides, mectin derivatives, morpholines,norpholines, n-phenyl carbamates, organotin compounds, oxathiincarboxamides, oxazoles, oxazolidine-diones, phenols, phenoxy quinolines,phenyl-acetamides, phenylamides, phenylbenzamides,phenyl-oxo-ethyl-thiophenes amides, phenylpyrroles, phenylureas,phosphorothiolates, phosphorus acids, phthalamic acids, phthalimides,picolinamides, piperazines, piperidines, plant extracts, polyoxins,propionamides, pthalimides, pyrazole-4-carboxamides, pyrazolinones,pyridazinones, pyridines, pyridine carboxamides, pyridinyl-ethylbenzamides, pyrimdinamines, pyrimidines, pyrimidine-amines,pyrimidione-hydrazone, pyrrolidines, pyrrolquinoliones, quinazolinones,quinolines, quinoline derivatives, quinoline-7-carboxylic acids,quinoxalines, spiroketalamines, strobilurins, sulfamoyl triazoles,sulphamides, tetrazolyloximes, thiadiazines, thiadiazole carboxamides,thiazole carboxanides, thiocyanates, thiophene carboxamides, toluamides,triazines, triazobenthiazoles, triazoles, triazole-thiones,triazolo-pyrimidylamine, valinamide carbamates, ammonium methylphosphonates, arsenic-containing compounds, benyimidazolylcarbamates,carbonitriles, carboxanilides, carboximidamides, carboxylicphenylamides, diphenyl pyridines, furanilides, hydrazine carboxamides,imidazoline acetates, isophthalates, isoxazolones, mercury salts,organomercury compounds, organophosphates, oxazolidinediones,pentylsulfonyl benzenes, phenyl benzamides, phosphonothionates,phosphorothioates, pyridyl carboxamides, pyridyl furfuryl ethers,pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines.

A further aspect of invention is related to a method of controlling orpreventing an infestation of plants, e.g. useful plants such as cropplants, propagation material thereof, e.g. seeds, harvested crops, e.g.harvested food crops, or of non-living materials by phytopathogenic orspoilage microorganisms or organisms potentially harmful to man,especially fungal organisms, which comprises the application of acompound of formula (I) or of a preferred individual compound asabove-defined as active ingredient to the plants, to parts of the plantsor to the locus thereof, to the propagation material thereof, or to anypart of the non-living materials.

Controlling or preventing means reducing infestation by insects or byphytopathogenic or spoilage microorganisms or organisms potentiallyharmful to man, especially fungal organisms, to such a level that animprovement is demonstrated.

A preferred method of controlling or preventing an infestation of cropplants by phytopathogenic microorganisms, especially fungal organisms,or insects which comprises the application of a compound of formula (I),or an agrochemical composition which contains at least one of saidcompounds, is foliar application. The frequency of application and therate of application will depend on the risk of infestation by thecorresponding pathogen or insect. However, the compounds of formula (I)can also penetrate the plant through the roots via the soil (systemicaction) by drenching the locus of the plant with a liquid formulation,or by applying the compounds in solid form to the soil, e.g. in granularform (soil application). In crops of water rice such granulates can beapplied to the flooded rice field. The compounds of formula (I) may alsobe applied to seeds (coating) by impregnating the seeds or tubers eitherwith a liquid formulation of the fungicide or coating them with a solidformulation.

A formulation, e.g. a composition containing the compound of formula(I), and, if desired, a solid or liquid adjuvant or monomers forencapsulating the compound of formula (I), may be prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally, surfaceactive compounds (surfactants).

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is preferably 1 g to 2000 g of active ingredient per hectare,more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha. Whenused as seed drenching agent, convenient dosages are from 10 mg to 1 gof active substance per kg of seeds.

When the combinations of the present invention are used for treatingseed, rates of 0.001 to 50 g of a compound of formula (I) per kg ofseed, preferably from 0.01 to 10 g per kg of seed are generallysufficient.

Suitably, a composition comprising a compound of formula (I) accordingto the present invention is applied either preventative, meaning priorto disease development or curative, meaning after disease development.

The compositions of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oilmiscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixingthe active ingredients with appropriate formulation inerts (diluents,solvents, fillers and optionally other formulating ingredients such assurfactants, biocides, anti-freeze, stickers, thickeners and compoundsthat provide adjuvancy effects). Also conventional slow releaseformulations may be employed where long lasting efficacy is intended.Particularly formulations to be applied in spraying forms, such as waterdispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like),wettable powders and granules, may contain surfactants such as 5 wettingand dispersing agents and other compounds that provide adjuvancyeffects, e.g. the ondensation product of formaldehyde with naphthalenesulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkylsulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least the compound of formula (I) together withcomponent (B) and (C), and optionally other active agents, particularlymicrobiocides or conservatives or the like. Concentrated forms ofcompositions generally contain in between about 2 and 80%, preferablybetween about 5 and 70% by weight of active agent. Application forms offormulation may for example contain from 0.01 to 20% by weight,preferably from 0.01 to 5% by weight of active agent. Whereas commercialproducts will preferably be formulated as concentrates, the end userwill normally employ diluted formulations.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

EXAMPLES

The Examples which follow serve to illustrate the invention. Certaincompounds of the invention can be distinguished from known compounds byvirtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the Examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppmor 0.2 ppm.

Throughout this description, temperatures are given in degrees Celsiusand “m.p.” means melting point. LC/MS means Liquid Chromatography MassSpectroscopy and the description of the apparatus and the methods are:

Method G:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30 V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 m, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 1.2min; Flow (ml/min) 0.85

Method H:

Spectra were recorded on a Mass Spectrometer from Waters (SQD, SQDIISingle quadrupole mass spectrometer) equipped with an electrospraysource (Polarity: positive and negative ions), Capillary: 3.00 kV, Conerange: 30V, Extractor: 2.00 V, Source Temperature: 150° C., DesolvationTemperature: 350° C., Cone Gas Flow: 50 I/h, Desolvation Gas Flow: 650I/h, Mass range: 100 to 900 Da) and an Acquity UPLC from Waters: Binarypump, heated column compartment, diode-array detector and ELSD detector.Column: Waters UPLC HSS T3, 1.8 m, 30×2.1 mm, Temp: 60° C., DADWavelength range (nm): 210 to 500, Solvent Gradient: A=water+5%MeOH+0.05% HCOOH, B=Acetonitrile+0.05% HCOOH, gradient: 10-100% B in 2.7min; Flow (ml/min) 0.85

Method W:

Spectra were recorded on a Mass Spectrometer (ACQUITY UPLC) from Waters(SQD, SQDII Single quadrupole mass spectrometer) equipped with anelectrospray source (Polarity: positive or negative ions, Capillary: 3.0kV, Cone: 30V, Extractor: 3.00 V, Source Temperature: 150° C.,Desolvation Temperature: 400° C., Cone Gas Flow: 60 L/Hr, DesolvationGas Flow: 700 L/Hr, Mass range: 140 to 800 Da), DAD Wavelength range(nm): 210 to 400, and an Acquity UPLC from Waters: Solvent degasser,binary pump, heated column compartment and diode-array detector. Column:Waters UPLC HSS T3, 1.8 m, 30×2.1 mm, Temp: 60° C., DAD Wavelength range(nm): 210 to 500, Solvent Gradient: A=Water/Methanol 9:1,0.1% formicacid, B=Acetonitrile+0.1% formic acid, gradient: 0-100% B in 2.5 min;Flow (ml/min) 0.75

Formulation Examples

Wettable powders a) b) c) active ingredient [compound of formula (I)]25% 50% 75% sodium lignosulfonate  5%  5% — sodium lauryl sulfate  3% — 5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenol polyethyleneglycol ether —  2% — (7-8 mol of ethylene oxide) highly dispersedsilicic acid  5% 10% 10% Kaolin 62% 27% —The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders that can be diluted with water to give suspensions of thedesired concentration.

Powders for dry seed treatment a) b) c) active ingredient [compound offormula (I)] 25% 50% 75% light mineral oil  5%  5%  5% highly dispersedsilicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20   The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording powders thatcan be used directly for seed treatment.

Emulsifiable concentrate active ingredient [compound of formula (I)] 10%octylphenol polyethylene glycol ether  3% (4-5 mol of ethylene oxide)calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 molof  4% ethylene oxide) Cyclohexanone 30% xylene mixture 50%Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredient [compound  5%  6%  4% of formula (I)]talcum 95% — — Kaolin — 94% — mineral filler — — 96%Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruder granules Active ingredient [compound 15% of formula (I)] sodiumlignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

Coated granules Active ingredient [compound of  8% formula (I)]polyethylene glycol (mol. wt. 200)  3% Kaolin 89%The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

Suspension concentrate active ingredient [compound of formula (I)] 40%propylene glycol 10% nonylphenol polyethylene glycol ether (15  6% molof ethylene oxide) Sodium lignosulfonate 10% carboxymethylcellulose  1%silicone oil (in the form of a 75% emulsion  1% in water) Water 32%The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredient [compound offormula 40% (I)] propylene glycol  5% copolymer butanol PO/EO  2%tristyrenephenole with 10-20 moles EO  2% 1,2-benzisothiazolin-3-one (inthe form 0.5%  of a 20% solution in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% 0.2%  emulsion in water) Water45.3%  The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the compound of formula (I) are mixed with2 parts of an aromatic solvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed.The obtained capsule suspension is stabilized by adding 0.25 parts of athickener and 3 parts of a dispersing agent. The capsule suspensionformulation contains 28% of the active ingredients. The medium capsulediameter is 8-15 microns.The resulting formulation is applied to seeds as an aqueous suspensionin an apparatus suitable for that purpose.

Preparation Examples Example 1: Preparation of2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamideStep 1: preparation of ethyl 2-benzyl-4,4,4-trifluoro-2-methyl-butanoate

n-Butyl lithium (2.5 M in hexanes, 100 mL, 248.9 mmol) was added slowlyto a solution of diisopropyl amine (35.2 mL, 248.9 mmol) intetrahydrofuran (400 mL) at −70° C. The resulting solution was aged for30 min at −70° C. and then ethyl 4,4,4-trifluorobutyrate (36 g, 207.4mmol) was added drop wise. The reaction was stirred for 2 h at −70° C.,benzyl bromide (43.2 g, 248.9 mmol) was added and the reaction mixturewas gradually warmed to room temperature over ca. 2 h. Saturated NH₄Clsolution was added and the mixture was extracted with methyl tertbutylether. The organic layer was washed with water, brine, dried over MgSO₄,filtrated and concentrated in vacuo. The residual oil was passed througha short pad of silica gel, the pad was rinsed with cyclohexane:ethylacetate (2:1) and the filtrate was concentrated in vacuo, affordingethyl 4,4,4-trifluoro-2-methyl-butanoate as light orange oil.

n-Butyl lithium (2.5 M in hexanes, 99 mL, 247.2 mmol) was added slowlyto a solution of diisopropyl amine (35 mL, 247.2 mmol) intetrahydrofuran (380 mL) at −70° C. The resulting solution was aged for30 min at −70° C. and then the crude product obtained above (49.5 g,190.2 mmol, diluted with tetrahydrofuran (30 mL)) was added slowly at−70° C. The resulting dark solution was stirred for 2 h at −70° C.before methyl iodide (13.1 mL, 209.3 mmol) was added. The reactionmixture was gradually warmed to 20° C. over ca. 3 h, then quenched withsaturated NH₄Cl solution and extracted with methyl tertbutylether. Theorganic layer was washed with water, brine, dried over MgSO₄, filtratedand concentrated in vacuo. The residual oil was passed through a shortpad of silica gel, the pad was rinsed with cyclohexane:ethyl acetate(2:1) and the filtrate was concentrated in vacuo, affording the titlecompound as light brown oil (ca. 80% pure).

¹H NMR (400 MHz, CDCl₃) δ 7.05-7.33 (m, 5H), 4.13 (q, 2H), 2.98 (d, 1H),2.81-2.72 (m, 2H), 2.11-2.32 (m, 1H), 1.28 (s, 3H), 1.21 (t, 3H).

Step 2: preparation of 2-benzyl-4,4,4-trifluoro-2-methyl-butanoic acid

A solution of ethyl 2-benzyl-4,4,4-trifluoro-2-methyl-butanoate (25.5 g,93.0 mmol) in 1,4-dioxane (45 mL)/ethanol (45 mL) was treated with NaOH(7.6 g, 186 mmol) at room temperature, the resulting solution was warmedto 90° C. and aged for 1 h at 90° C. After cooling to room temperature,the reaction mixture was concentrated to about 50% of the originalvolume. The residue was diluted with water and washed with cyclohexane.The water layer was then acidified with HCl (conc.) under ice cooling attemp <25° C. and the mixture was extracted with DCM. The organic layerwere washed with brine, dried with Na₂SO₄, filtrated and concentrated invacuo to afford 2-benzyl-4,4,4-trifluoro-2-methyl-butanoic acid as darkyellow oil which solidified upon standing at room temperature.

¹H NMR (400 MHz, CDCl₃) b 7.07-7.37 (m, 3H), 7.07-7.19 (m, 2H), 3.02 (d,1H), 2.86 (d, 1H), 2.70-2.83 (m, 1H), 2.17-2.35 (m, 1H), 1.31 (s, 3H).

Step 3: preparation of2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamide

Oxalyl chloride (0.15 mL, 1.66 mmol) was added to a solution of2-benzyl-4,4,4-trifluoro-2-methyl-butanoic acid (0.4 g, 1.38 mmol) and 2drops of dimethyl formamide in dichloromethane (4 mL) at roomtemperature. The resulting solution was stirred for 1 h at roomtemperature and then concentrated in vacuo an oily residue. This residuewas taken up in dichloromethane (2 mL) and slowly added to a solution of8-fluoro-quinolin-3-amine (0.22 g, 1.38 mmol), 4-dimethylaminopyridine(ca. 5 mg) and triethylamine (0.58 mL, 4.14 mmol) in dichloromethane (5mL). The resulting solution was stirred at room temperature overnight,diluted with ethyl acetate and quenched with water. The organic layerwas washed with aqueous NaHCO₃ and brine, dried over MgSO₄, filtratedand concentrated in vacuo. The residue was purified by chromatography onsilica gel to afford2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamide aslight brown foam.

¹H NMR (400 MHz, CDCl₃) b 8.73 (s, 1H), 8.44 (d, 1H), 7.62 (d, 1H),7.53-7.48 (m, 1H), 7.00-7.40 (m, 6H), 3.11-3.34 (m, 2H), 2.74 (d, 1H),2.21-2.45 (m, 1H), 1.53 (s, 3H).

Example 2: Preparation of2-benzyl-N-(8-fluoro-4-methyl-3-quinolyl)-2,4-dimethyl-pent-4-enamideStep 1: preparation of 8-fluoro-3-iodo-4-methyl-quinoline

To a suspension of 2-fluoroaniline (25 g, 214 mmol) and potassiumcarbonate (29.8 g, 214 mmol) in acetone (430 mL) was added1-bromo-2-butyne (26.1 g, 192 mmol) at room temperature. The resultingmixture was warmed to 70° C. and stirred for 22 h at this temperature.After cooling to room temperature, approx. 200 mL of the solvent wasremoved in vacuo and the water was added. The mixture was extracted withtertbutyl methyl ether, the organic layer was washed with water, brine,dried over Na₂SO₄, filtrated and concentrated in vacuo. The dark yellowresidue was filtrated through a plug of silica gel and the filtrate wasconcentrated to a yellow liquid consisting of a mixture ofN-but-2-ynyl-2-fluoro-aniline and N,N-bis(but-2-ynyl)-2-fluoro-aniline.

This oil was diluted with acetonitrile (2000 mL), NaHCO₃ (34.6 g, 408mmol) and iodine (104 g, 408 mmol) was added and the resulting darkbrown solution was stirred for 3 h at room temperature. Aqueous Na₂S₂O₃solution was then added and the mixture was extracted multiple timeswith ethyl acetate. The combined organic layers were washed with waterand brine; dried over Na₂SO₄, filtrated and concentrated in vacuo. Theresidue was purified by chromatography on silica gel to afford8-fluoro-3-iodo-4-methyl-quinoline as light yellow solid.

¹H NMR (400 MHz, CDCl₃) δ 9.15 (s, 1H), 7.77-7.91 (m, 1H), 7.51 (dt,1H), 7.36-7.47 (m, 1H), 2.87 (s, 3H).

¹⁹F NMR (377 MHz CDCl₃) δ −124.00 (s, 1F).

Step 2: preparation of 8-fluoro-4-methyl-quinolin-3-amine

A pressure resistant vessel was charged with8-fluoro-3-iodo-4-methyl-quinoline (1 g, 3.5 mmol), Cs₂CO₃ (2.3 g, 7.0mmol), pentane-2,4-dione (0.14 g, 1.4 mmol), copper(II)acetylacetonate(0.09 g, 0.35 mmol) and N,N-dimethylformamide (7 mL). The resultingmixture was purged with N₂, aqueous ammonia (25%, 1 mL, 14 mmol) wasthen added, and the vessel was sealed and warmed to 90° C. After stirredfor 24 h at 90° C., the resulting dark solution was cooled to roomtemperature, diluted with water and extracted several times with ethylacetate. The combined organic layers were washed with water and brine;dried over Na₂SO₄, filtrated and concentrated in vacuo. The residue waspurified by chromatography on silica gel to afford8-fluoro-4-methyl-quinolin-3-amine as brown solid.

¹H NMR (400 MHz, CDCl₃) b 8.51 (s, 1H), 7.63 (d, 1H), 7.40 (dt, 1H),7.14 (ddd, 1H), 3.93 (br s, 2H), 2.43 (s, 3H).

Step 3: preparation of methyl 2-methyl-3-phenyl-propanoate

A solution of methyl-3-phenylpropionate (5.0 g, 30 mmol) intetrahydrofuran (15 mL) was added slowly to lithium diisopropylamide(prepared from n-butyl lithium [2.5 M in hexanes, 14 mL, 36 mmol] anddiisopropylamine [5.2 mL, 37 mmol] in tetrahydrofuran [15 mL]) at −78°C. The reaction was aged for 2 h at −78° C., iodomethane (2.8 mL, 45mmol) was added and the resulting solution was gradually warmed to 0° C.over 3 h. Saturated, aq. NH₄Cl solution was then added and the mixturewas extracted with tertbutyl methyl ether. The organic layer was washedwith brine, dried over Na₂SO₄, filtrated and concentrated in vacuo. Theresidue was purified by chromatography on silica gel to afford methyl2-methyl-3-phenyl-propanoate as colourless liquid.

¹H NMR (400 MHz, CDCl₃) δ 6.98-7.29 (m, 5H), 3.56 (s, 3H), 2.96 (dd,1H), 2.53-2.73 (m, 2H), 1.08 (d, 3H).

Step 4: preparation of methyl 2-benzyl-2,4-dimethyl-pent-4-enoate

A solution of methyl 2-methyl-3-phenyl-propanoate (1.40 g, 7.86 mmol) intetrahydrofuran (4 mL) was added slowly to lithium diisopropylamide(prepared from n-butyl lithium [2.5 M in hexanes, 3.8 mL, 9.4 mmol] anddiisopropylamine [1.38 mL, 9.8 mmol] in tetrahydrofuran [4 mL]) at −78°C. The reaction was aged for 2 h at −78° C., 3-bromo-2-methylpropene(1.22 mL, 11.8 mmol) was added and the resulting solution was graduallywarmed to 0° C. over 3 h. Saturated, aq. NH₄Cl solution was then addedand the mixture was extracted with tertbutyl methyl ether. The organiclayer was washed with brine, dried over Na₂SO₄, filtrated andconcentrated in vacuo. The residue was purified by chromatography onsilica gel to afford methyl 2-benzyl-2,4-dimethyl-pent-4-enoate ascolourless liquid.

¹H NMR (400 MHz, CDCl₃) δ 6.98-7.43 (m, 5H), 4.87 (s, 1H), 4.72 (s, 1H),3.68 (s, 2H), 3.14 (d, 1H), 2.69 (t, 2H), 2.18 (d, 1H), 1.71 (s, 3H),1.12 (s, 3H).

Step 5: preparation of2-benzyl-N-(8-fluoro-4-methyl-3-quinolyl)-2,4-dimethyl-pent-4-enamide

To a suspension of methyl 2-benzyl-2,4-dimethyl-pent-4-enoate (0.10 g,0.5 mmol) and 8-fluoro-4-methyl-quinolin-3-amine (0.08 g, 0.5 mmol) intoluene (1 mL) was added trimethyl aluminium (2 M in toluene, 0.3 mL,0.6 mmol) at room temperature. The resulting mixture was warmed to 90°C. and stirred for 64 h at this temperature. The reaction was thencooled to room temperature and added into aq. NaOH (1 M) solution. Themixture was extracted with ethyl acetate, the organic layer was washedwith brine, dried over Na₂SO₄, filtrated and concentrated in vacuo. Theresidue was purified by chromatography on silica gel to afford2-benzyl-N-(8-fluoro-4-methyl-3-quinolyl)-2,4-dimethyl-pent-4-enamide asyellow solid, m.p. 105-109° C.

¹H NMR (400 MHz, CDCl₃) δ 8.83 (s, 1H), 7.73 (d, 1H), 7.53-7.48 (m, 1H),6.99-7.45 (m, 7H), 4.99 (s, 1H), 4.89 (s, 1H), 3.35 (d, 1H), 3.02 (d,1H), 2.66 (d, 1H), 2.29 (s, 3H), 2.22 (d, 1H), 1.86 (s, 3H), 1.42 (s,3H)

¹⁹F NMR (377 MHz CDCl₃) δ −124.67 (s, 1F)

Example 3: Preparation of2-benzyl-2,4-dimethyl-N-(3-quinolyl)pentanamide Step 1: preparation ofethyl 2-benzyl-2,4-dimethyl-pentanoate

A solution of ethyl 2,4-dimethylpentanoate (1.0 g, 5.1 mmol, preparedaccording to Synthesis, 2005, p. 272-278) in tetrahydrofuran (5 mL) wasadded slowly to lithium diisopropylamide (prepared from n-butyl lithium[1.6 M in hexanes, 3.8 mL, 6.1 mmol] and diisopropylamine [0.85 mL, 6.1mmol] in tetrahydrofuran [5 mL]) at −78° C. The reaction was aged for 2h at −78° C., benzylbromide (0.95 g, 5.56 mmol) and1,3-Dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone (0.1 mL) was addedand the resulting solution was gradually warmed to 20° C. over 3 h.Saturated, aq. NH₄Cl solution was then added and the mixture wasextracted with tertbutyl methyl ether. The organic layer was washed withbrine, dried over Na₂SO₄, filtrated and concentrated in vacuo. Theresidue was purified by chromatography on silica gel to afford ethyl2-benzyl-2,4-dimethyl-pentanoate as colourless liquid.

¹H NMR (400 MHz, CDCl₃) δ 7.02-7.26 (m, 5H), 4.07 (q, 2H), 3.03 (d, 1H),2.60 (d, 1H), 1.64-1.91 (m, 2H), 1.38 (dd, 1H), 1.22 (t, 3H), 1.09 (s,3H), 0.91 (d, 3H), 0.83 (d, 3H).

Step 2: preparation of 2-benzyl-2,4-dimethyl-N-(3-quinolyl)pentanamide

To a suspension of ethyl 2-benzyl-2,4-dimethyl-pentanoate (0.09 g, 0.35mmol) and quinolin-3-amine (0.05 g, 0.35 mmol) in toluene (0.7 mL) wasadded trimethyl aluminium (2 M in toluene, 0.22 mL, 0.45 mmol) at roomtemperature. The resulting solution was warmed to 90° C. and stirred for24 h at this temperature. The reaction was then cooled to roomtemperature and added into aq. NaOH (1 M) solution. The mixture wasextracted with ethyl acetate, the organic layer was washed with brine,dried over Na₂SO₄, filtrated and concentrated in vacuo. The residue waspurified by chromatography on silica gel to afford2-benzyl-2,4-dimethyl-N-(3-quinolyl)pentanamide as yellow solid, m.p.147-148° C.

¹H NMR (400 MHz, CDCl₃) δ 8.66 (d, 1H), 8.43 (d, 1H), 8.03 (d, 1H), 7.81(dd, 1H), 7.44-7.72 (m, 2H), 7.05-7.23 (m, 5H), 3.19 (d, 1H), 2.64 (d,1H), 2.05 (dd, 1H), 1.73-1.92 (m, 1H), 1.45-1.52 (m, 1H), 1.34 (s, 3H),1.00 (d, 3H), 0.92 (d, 3H).

Example 4: Preparation of the Single Isomers(S)-2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamideand(R)-2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamide

The 2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamidemixture was submitted to chiral resolution by preparative HPLCchromathography using the conditions outlined hereafter.

Analytical HPLC Method

SFC:Waters Acquity UPC²/QDa

PDA Detector Waters Acquity UPC²

Column: Daicel SFC CHIRALPAK® OZ, 3 um, 0.3 cm×10 cm, 40° C.

Mobile phase: A: CO2 B: EtOH gradient: 20% B in 1.8 min

ABPR: 1800 psi

Flow rate: 2.0 ml/min

Detection: 250 nm

Sample concentration: 1 mg/mL in ACN/iPr 50/50

Injection: 1 uL

Preparative HPLC Method:

Autopurification System from Waters: 2767 sample Manager, 2489UV/Visible Detector, 2545 Quaternary Gradient Module.

Column: Daicel CHIRALPAK® IB, 5 um, 1.0 cm×25 cm

Mobile phase: Hept/EtOH 90/10

Flow rate: 10 ml/min

Detection: UV 265 nm

Sample concentration: 100 mg/mL in MeOH/DCM (1/1)

Injection: 250 μl

Results (Analytical Method/Preparative Method):

First eluting enantiomer Second eluting enantiomer Retention time (min)~0.78/~3.71 Retention time (min) ~1.60/~5.99 Chemical purity (area % at220 Chemical purity (area % at 220 nm) 99 nm) 99 Enantiomeric excess(%) > 99 Enantiomeric excess (%) > 99

The compound with the elution time of 0.78 minute is(2R)-2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamide,corresponding to compound F-24.

The compound with the elution time of 1.60 minutes is(2S)-2-benzyl-4,4,4-trifluoro-N-(8-fluoro-3-quinolyl)-2-methyl-butanamide,corresponding to compound F-23.

TABLE E Physical data of compounds of formula (I) RT [M + H] MP EntryIUPAC name STRUCTURE (min) (measured) Method ° C. E-12-benzyl-2-fluoro-N-(8- fluoro-3-quinolyl)-4- methyl-pentanamide

1.12 370 G E-2 2-benzyl-N-(8-fluoro-2- methyl-3-quinolyl)-2-methyl-pent-4-ynamide

1.07 361 G E-3 2-benzyl-N-(8-fluoro-4- methyl-3-quinolyl)-2-methyl-pent-4-ynamide

1.08 397 G 61-65 E-4 2-benzyl-4-chloro-N-(8- fluoro-2-methyl-3-quinolyl)pent-4-enamide

1.08 383 G 96-99 E-5 2-benzyl-4-chloro-N-(8- fluoro-4-methyl-3-quinolyl)pent-4-enamide

1.04 383 G 53-58 E-6 2-benzyl-4-chloro-N-(8- fluoro-3-quinolyl)pent-4-enamide

1.08 369 G 166-168 E-7 2-[(3- fluorophenyl)methyl]-N-(8-fluoro-3-quinolyl)-2,4- dimethyl-pentanamide

1.17 384 G E-8 4,4,4-trifluoro-N-(8- fluoro-2-methyl-3- quinolyl)-2-[(3-fluorophenyl)methyl]-2- methyl-butanamide

1.08 423 G E-9 2-benzyl-N-(8-chloro-3- quinolyl)-2,4-dimethyl-pentanamide

1.21 381 G 163-165 E-10 N-(8-fluoro-2-methyl-3- quinolyl)-2-[(3-fluorophenyl)methyl]-2,4- dimethyl-pentanamide

1.18 398 G 93-95 E-11 2-[(3- fluorophenyl)methyl]-N-(8-fluoro-3-quinolyl)-2,4- dimethyl-pent-4-enamide

1.14 381 G 125-127 E-12 N-(8-fluoro-2-methyl-3- quinolyl)-2-[(3-fluorophenyl)methyl]-2,4- dimethyl-pent-4-enamide

1.15 396 G 124-126 E-13 2-benzyl-N-(8-chloro-2- methyl-3-quinolyl)-2,4-dimethyl-pentanamide

1.26 396 G  99-100 E-14 2-benzyl-N-(8-chloro-4- methyl-3-quinolyl)-2,4-dimethyl-pentanamide

1.18 395 G 124-126 E-15 2-benzyl-N-(8-chloro-4-methyl-3-quinolyl)-4,4,4- trifluoro-2-methyl- butanamide

1.10 421 G 73-75 E-16 4,4,4-trifluoro-N-(8- fluoro-2-methyl-3-quinolyl)-2-[(4- fluorophenyl)methyl]-2- methyl-butanamide

1.09 424 G E-17 2-benzyl-N-(8-chloro-2- methyl-3-quinolyl)-4,4,4-trifluoro-2-methyl- butanamide

1.15 421 G 47-50 E-18 4,4,4-trifluoro-2-[(4- fluorophenyl)methyl]-N-(8-fluoro-3-quinolyl)-2- methyl-butanamide

1.08 409 G E-19 2-benzyl-N-(8-fluoro-4- methyl-3-quinolyl)-4-methyl-pentanamide

1.07 365 G E-20 2-benzyl-4-chloro-N-(8- fluoro-4-methyl-3-quinolyl)-2-methyl-pent- 4-enamide

1.08 397 G 124-126 E-21 2-benzyl-4-chloro-N-(8- fluoro-2-methyl-3-quinolyl)-2-methyl-pent- 4-enamide

1.12 397 G 121-123 E-22 4,4,4-trifluoro-2-[(3- fluorophenyl)methyl]-N-(8-fluoro-3-quinolyl)-2- methyl-butanamide

1.08 410 G E-23 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methyl-4-(trifluoromethyl)pent-4- enamide

1.13 418 G E-24 2-benzyl-N-(8-fluoro-3- quinolyl)-3-(trifluoromethyl)but-3- enamide

1.75 389 H E-25 2-benzyl-3-(1- fluorocyclopropyl)-N-(8-fluoro-3-quinolyl)-2- methyl-propanamide

1.07 381 G 162-164 E-26 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methyl-pent-4-ynamide

1.02 347 G 189-191 E-27 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methyl-hexanamide

1.20 365 G 135-137 E-28 (Z)-2-benzyl-N-(8-fluoro-3-quinolyl)-2-methyl-hex- 4-enamide

1.12 363 G 128-130 E-29 2-benzyl-N-(8-fluoro-3- quinolyl)hex-4-ynamide

1.04 347 G 218-220 E-30 2-benzyl-N-(8-fluoro-3-quinolyl)-2-methyl-hex-4- ynamide

1.07 361 G 136-138 E-31 N-(8-fluoro-3-quinolyl)-2- methyl-3-phenyl-propanamide

0.97 309 G 188-190 E-32 (E)-2-benzyl-N-(8-fluoro-3-quinolyl)-2,4-dimethyl- hex-4-enamide

1.16 377 G E-33 2-benzyl-4,4,4-trifluoro- N-(8-fluoro-3-quinolyl)-N-(methoxymethyl)-2- methyl-butanamide

1.11 435 G 108-110 E-34 2-benzyl-5,5-difluoro-N-(8-fluoro-3-quinolyl)-2- methyl-pentanamide

1.05 387 G E-35 2-benzyl-N-(8-fluoro-3- quinolyl)-4-methyl- pentanamide

1.10 365 G 89-91 E-36 2-benzyl-N-(8-fluoro-3- quinolyl)-2,4-dimethyl-hexanamide

0.90 377 G E-37 2-benzyl-N-(8-fluoro-2- methyl-3-quinolyl)-2-methoxy-4-methyl- pentanamide

1.21 395 G 92-94 E-38 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methoxy-4-methyl-pentanamide

1.15 381 G 133-135 E-39 N-(8-fluoro-2-methyl-3-quinolyl)-2-isopropoxy-2- methyl-3-phenyl- propanamide

1.18 381 G E-40 N-(8-fluoro-3-quinolyl)-2- isopropoxy-2-methyl-3-phenyl-propanamide

1.13 367 G E-41 N-(8-fluoro-2-methyl-3- quinolyl)-2-methoxy-2-methyl-3-phenyl- propanamide

1.05 353 G E-42 2-benzyl-4,4,4-trifluoro- N-(8-fluoro-3-quinolyl)-N,2-dimethyl-butanamide

1.10 405 G 137-139 E-43 N-(8-fluoro-3-quinolyl)-2- methoxy-2-methyl-3-phenyl-propanamide

1.00 339 G 107-109 E-44 2-benzyl-4,4,4-trifluoro-N-(8-fluoro-2-methyl-3- quinolyl)butanamide

1.04 391 G E-45 2-benzyl-4,4,4-trifluoro- N-(8-fluoro-4-methyl-3-quinolyl)butanamide

1.00 391 G 165-167 E-46 2-benzyl-2-ethyl-N-(8- fluoro-3-quinolyl)-4-methyl-pent-4-enamide

1.17 377 G E-47 2-benzyl-4,4,4-trifluoro- N-(8-fluoro-2-methyl-3-quinolyl)-2-methyl- butanamide

1.07 405 G 130-132 E-48 2-benzyl-N-(8-fluoro-3- quinolyl)-2,4-dimethyl-pent-3-enamide

1.14 363 G 167-169 E-49 2-benzyl-4,4,4-trifluoro-N-(5-fluoro-3-quinolyl)-2- methyl-butanamide

1.10 392 G 140-142 E-50 2-benzyl-4,4,4-trifluoro-N-(8-fluoro-4-methyl-3- quinolyl)-2-methyl- butanamide

1.05 406 G 106-109 E-51 2-benzyl-N-(8-chloro-3-quinolyl)-4,4,4-trifluoro-2- methyl-butanamide

1.13 408 G 104-106 E-52 2-benzyl-4,4,4-trifluoro-N-(7-fluoro-3-quinolyl)-2- methyl-butanamide

1.09 392 G 180-182 E-53 2-benzyl-4-chloro-N-(8- fluoro-3-quinolyl)-2-methyl-pent-4-enamide

1.09 383 G 148-150 E-54 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methyl-4-methylene-hexanamide

1.17 377 G 118-120 E-55 2-benzyl-4,4-difluoro-N-(8-fluoro-3-quinolyl)-2- methyl-butanamide

1.03 373 G E-56 2-benzyl-4-chloro-4,4- difluoro-N-(8-fluoro-3-quinolyl)-2-methyl- butanamide

1.10 408 G E-57 2-benzyl-4,4-difluoro-N- (8-fluoro-3-quinolyl)-2-methyl-but-3-enamide

1.08 371 G E-58 2-benzyl-4-chloro-4,4- difluoro-N-(8-fluoro-3-quinolyl)butanamide

1.06 395 G 65-70 E-59 2-benzyl-4,4,4-trifluoro-2- methyl-N-(8-methyl-3-quinolyl)butanamide

1.14 387 G 123-125 E-60 2-benzyl-N-(7,8-difluoro-3-quinolyl)-4,4,4-trifluoro- 2-methyl-butanamide

1.12 409 G 183-186 E-61 2-benzyl-N-(8-fluoro-3- quinolyl)-N-methoxy-2,4-dimethyl-pentanamide

1.25 396 G E-62 2-benzyl-N-(6-methoxy- 3-quinolyl)-2,4-dimethyl-pent-4-enamide

1.08 376 G E-63 2-benzyl-N-(8-bromo-3- quinolyl)-2,4-dimethyl-pent-4-enamide

1.20 425 G 165-169 E-64 2-benzyl-2,4-dimethyl-N- (3-quinolyl)pent-4-enamide

1.09 346 G E-65 2-benzyl-N-(8-fluoro-4- methyl-3-quinolyl)-2,4-dimethyl-pent-4-enamide

1.11 378 G 105-109 E-66 2-benzyl-N-(8-fluoro-2- methyl-3-quinolyl)-2,4-dimethyl-pent-4-enamide

1.16 378 G E-67 N-(8-fluoro-3-quinolyl)-N- isobutoxy-2,2-dimethyl-3-phenyl-propanamide

1.28 395 G E-68 2-benzyl-4,4-difluoro-N- (8-fluoro-3-quinolyl)-2-methyl-pentanamide

1.06 387 G 156-158 E-69 N-(8-fluoro-3-quinolyl)- 2,2-dimethyl-3-phenyl-propanamide

1.04 323 G E-70 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methyl-3-(1-methylcyclopropyl) propanamide

1.17 377 G 149-151 E-71 2-benzyl-4-fluoro-N-(8- fluoro-3-quinolyl)-2-methyl-pent-4-enamide

1.06 367 G 132-134 E-72 2-benzyl-3-(2,2- difluorocyclopropyl)-N-(8-fluoro-3-quinolyl)-2- methyl-propanamide

1.10 399 G E-73 2-benzyl-3-(2,2- difluorocyclopropyl)-N-(8-fluoro-3-quinolyl)-2- methyl-propanamide

1.09 400 G E-74 2-benzyl-N-(8-fluoro-3- quinolyl)-2,4-dimethyl-pent-4-enamide

1.13 363 G 147-149 E-75 2-benzyl-3-(2,2- dichlorocyclopropyl)-N-(8-fluoro-3-quinolyl)-2- methyl-propanamide

1.17 431 G E-76 2-benzyl-3-cyclopropyl- N-(8-fluoro-3-quinolyl)-2-methyl-propanamide

1.12 363 G 157-159 E-77 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methyl-pentanamide

1.06 387 G 156-158 E-78 2-benzyl-N-(8-fluoro-3- quinolyl)-2-methyl-pent-4-enamide

1.08 349 G 146-149 E-79 2-benzyl-4,4,4-trifluoro-N-(3-quinolyl)butanamide

1.00 359 G E-80 2-benzyl-4,4,4-trifluoro- N-(8-fluoro-3-quinolyl)-2-methyl-butanamide

1.08 391 G E-81 2-benzyl-4,4,4-trifluoro-2- methyl-N-(3-quinolyl)butanamide

1.03 373 G E-82 2-benzyl-4,4,4-trifluoro- N-(8-fluoro-3-quinolyl)butanamide

1.03 377 G 161-164 E-83 2-benzyl-2-cyano-N-(8- fluoro-3-quinolyl)-4-methyl-pentanamide

1.14 376 G E-84 2-benzyl-N-(8-fluoro-4- methyl-3-quinolyl)-2,4-dimethyl-pentanamide

0.88 379 G 73-79 E-85 2-benzyl-2,4-dimethyl-N- (3-quinolyl)pentanamide

0.88 347 G 147-148 E-86 2-benzyl-N-(8-fluoro-2- methyl-3-quinolyl)-2,4-dimethyl-pentanamide

0.95 379 G E-87 2-benzyl-N-(8-fluoro-3- quinolyl)-2,4-dimethyl-pentanamide

1.15 365 G 140-142 E-88 2-benzyl-N-(8-fluoro-3- quinolyl)-3,3-dimethyl-butanamide

0.98 351 G 212-215 E-89 2-benzyl-N-(8-fluoro-2- methyl-3-quinolyl)-3-(1-methylcyclopropyl) propanamide

1.12 377 G 162-163 E-90 2-benzyl-N-(8-fluoro-4- methyl-3-quinolyl)-3-(1-methylcyclopropyl) propanamide

1.07 377 G 144-146 E-91 2-benzyl-N-(8-fluoro-3- quinolyl)-3-(1-methylcyclopropyl) propanamide

1.12 363 G 135-136 E-92 2-benzyl-N-(8-fluoro-2- methyl-3-quinolyl)-4-methyl-pent-4-enamide

1.08 363 G 97-99 E-93 2-benzyl-N-(8-fluoro-4- methyl-3-quinolyl)-4-methyl-pent-4-enamide

1.05 363 G 116-118 E-94 2-benzyl-N-(8-fluoro-3- quinolyl)-4-methyl-pent-4-enamide

1.08 349 G 170-172 E-95 2-benzyl-N-(8-fluoro-2- methyl-3-quinolyl)-3-(1-methylcyclopropyl) propanamide

0.94 347 G

TABLE F Physical data of compounds of formula (I) as individualenantiomers RT MP Entry IUPAC name STRUCTURE [α]D₂₀ (min) [M + H] Method° C. F-1 (2S)-2-benzyl-N- (8-fluoro-2- methyl-3- quinolyl)-2,4-dimethyl-pent-4- enamide

3.55 378 Column: Daicel CHIRALPAK ® ID, 5 μm, 2.0 cm x 25 cm Mobilephase: A: CO2 B: iPr isocratic: 15% B in 15 min F-2 (2R)-2-benzyl-N-(8-fluoro-2- methyl-3- quinolyl)-2,4- dimethyl-pent-4- enamide

2.44 378 Backpressure: 150 bar Flow rate: 60 ml/min GLS pump: 5 ml/minMeOH Detection: UV 254 nm Sample concentration: 54 mg/mL in MeOHInjection: 200-400 μl F-3 (2S)-2-benzyl-N- (8-fluoro-4- methyl-3-quinolyl)-2,4- dimethyl- pentanamide

4.23 Column: Daicel CHIRALPAK ® IF, 5 μm, 2.0 cm × 25 cm Mobile phase:A: CO2 B: EtOH isocratic: 30% B in 30 min F-4 (2R)-2-benzyl-N-(8-fluoro-4- methyl-3- quinolyl)-2,4- dimethyl- pentanamide

3.13 Backpressure: 150 bar Flow rate: 60 ml/min GLS pump: 3 ml/min MeOHDetection: UV 235 nm Sample concentration: 47 mg/mL in MeOH Injection:200-400 μl F-5 (2S)-2-benzyl-N- (8-fluoro-4- methyl-3- quinolyl)-2,4-dimethyl-pent-4- enamide

10.99 377 Column: Daicel CHIRALPAK ® ID, 5 μm, 1.0 cm × 25 cm Mobilephase: Heptane/ EtOAc 70/30 Flow rate: 10 ml/min F-6 (2R)-2-benzyl-N-(8-fluoro-4- methyl-3- quinolyl)-2,4- dimethyl-pent-4- enamide

7.67 377 Detection: UV 265 nm Sample concentration: 15 mg/mL in EE,filtered Injection: 300 μl F-7 (2S)-2-benzyl-N- (8-fluoro-2- methyl-3-quinolyl)-2,4- dimethyl- pentanamide

7.02 379 Column: Daicel CHIRALPAK ® ID, 5 μm, 1.0 cm × 25 cm Mobilephase: Hept/iPr 80/20 Flow rate: 10 ml/min Detection: F-8(2R)-2-benzyl-N- (8-fluoro-2- methyl-3- quinolyl)-2,4- dimethyl-pentanamide

3.99 379 UV 265 nm Sample concentration: 93 mg/mL in DCM Injection:50-80 μl F-9 (2R)-2-benzyl-N- (8-fluoro-3- quinolyl)-2- methyl-3-(1-methylcyclopropyl) propanamide

2.68 377 Column: Daicel CHIRALPAK ® IA, 5 μm, 1.0 cm × 25 cm Mobilephase: TBME/EtOH 98/02 Flow rate: 10 ml/min  62-  64 F- 10(2S)-2-benzyl-N- (8-fluoro-3- quinolyl)-2- methyl-3-(1-methylcyclopropyl) propanamide

4.72 377 Detection: UV 220 nm Sample concentration: 42 mg/mL in DCMInjection: 120-240 μl  58-  60 F- 11 (2R)-2-benzyl- 4,4,4-trifluoro-N-(8-fluoro-2- methyl-3- quinolyl)-2- methyl- butanamide

12.76 405 Column: Daicel CHIRALPAK ® IE, 5 μm, 1.0 cm × 25 cm Mobilephase: Hept/EtOH 95/05 Flow rate: 10 ml/min 137- 139 F- 12(2S)-2-benzyl- 4,4,4-trifluoro-N- (8-fluoro-2- methyl-3- quinolyl)-2-methyl- butanamide

9.16 405 Detection: UV 265 nm Sample concentration: 142 mg/mL in DCMInjection: 35 μl-110 μl 135- 136 F- 13 (2R)-2-benzyl- 4,4,4-trifluoro-N-(8-fluoro-4- methyl-3- quinolyl)-2- methyl- butanamide

14.12 405 Column: Daicel CHIRALPAK ® IF, 5 μm, 1.0 cm × 25 cm Mobilephase: Hept/EtOH 90/10 Flow rate: 10 ml/min  71-  73 F- 14(2S)-2-benzyl- 4,4,4-trifluoro-N- (8-fluoro-4- methyl-3- quinolyl)-2-methyl- butanamide

5.67 405 Detection: UV 265 nm Sample concentration: 250 mg/mL in DCMInjection: 100 μl  74-  76 F- 15 (2S)-2-benzyl-N- (7,8-difluoro-3-quinolyl)-4,4,4- trifluoro-2-methyl- butanamide

−236 4.40 409 Column: Daicel CHIRALPAK ® IA, 5 μm, 1.0 cm × 25 cm Mobilephase: TBME/EtOH 95/05 Flow rate: 10 ml/min F- 16 (2R)-2-benzyl-N-(7,8-difluoro-3- quinolyl)-4,4,4- trifluoro-2-methyl- butanamide

+241 2.74 409 Detection: UV 265 nm Sample concentration: 37 mg/mL in EEInjection: 130 μl F- 17 (2S)-2-benzyl- 4,4,4-trifluoro-2- methyl-N-(8-methyl-3- quinolyl)butanamide

−245 9.81 387 Column: Daicel CHIRALPAK ® IB, 5 μm, 1.0 cm × 25 cm Mobilephase: Hept/iPr 95/05 Flow rate: 10 ml/min F- 18 (2R)-2-benzyl-4,4,4-trifluoro-2- methyl-N-(8- methyl-3- quinolyl)butanamide

+267 6.52 387 Detection: UV 265 nm Sample concentration: 30 mg/mL in EE,filtered!! Injection: 160-200 μl F- 19 (2R)-2-benzyl-N- (8-fluoro-3-quinolyl)-2,4- dimethyl- pentanamide

12.13 365 Column: Daicel CHIRALPAK ® IB, 5 μm, 1.0 cm × 25 cm Mobilephase: Hept/iPr 90/10 Flow rate: 10 ml/min F- 20 (2S)-2-benzyl-N-(8-fluoro-3- quinolyl)-2,4- dimethyl- pentanamide

4.45 365 Detection: UV 265 nm Sample concentration: 20 mg/mL in ACNfiltered Injection: 500 μl F- 21 (2S)-2-benzyl-N- (8-fluoro-3-quinolyl)-2,4- dimethyl-pent-4- enamide

5.01 363 Column: Daicel CHIRALPAK ® IB, 5 μm, 1.0 cm × 25 cm Mobilephase: Hept/EtOH 90/10 Flow rate: 10 ml/min Detection: 132- 135 F- 22(2R)-2-benzyl-N- (8-fluoro-3- quinolyl)-2,4- dimethyl-pent-4- enamide

3.18 363 UV 265 nm Sample concentration: 10 mg/mL in MeOH/DCM (1/1)Injection: 250 μl 133- 135 F- 23 (2S)-2-benzyl- 4,4,4-trifluoro-N-(8-fluoro-3- quinolyl)-2- methyl- butanamide

5.99 391 Column: Daicel CHIRALPAK ® IB, 5 μm, 1.0 cm × 25 cm Mobilephase: Hept/EtOH 90/10 Flow rate: 10 ml/min Detection: F- 24(2R)-2-benzyl- 4,4,4-trifluoro-N- (8-fluoro-3- quinolyl)-2- methyl-butanamide

3.71 391 UV 265 nm Sample concentration: 10 mg/mL in MeOH/DCM (1/1)Injection: 250 μl F- 25 (2R)-2-benzyl-4- chloro-N-(8- fluoro-2-methyl-3-quinolyl)pent-4- enamide

3.10 383 Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK ® ID, 5 μm, 2.0cm × 25 cm Mobile phase: A: CO2 B: iPr isocratic: 15% B in F- 26(2S)-2-benzyl-4- chloro-N-(8- fluoro-2-methyl-3- quinolyl)pent-4-enamide

4.32 383 20 min Backpressure: 150 bar Flow rate: 60 ml/min GLS pump: 4ml/min EtOAc Detection: UV 235 nm Sample concentration: 19 mg/mL in MeOHInjection: 200-500 μl F- 27 (2R)-2-benzyl-4- chloro-N-(8-fluoro-4-methyl-3- quinolyl)pent-4- enamide

1.16 383 Sepiatec Prep SFC 100 Column: Daicel CHIRALPAK ® ID, 5 μm, 2.0cm × 25 cm Mobile phase: A: CO2 B: iPr isocratic: 35% B in F- 28(2S)-2-benzyl-4- chloro-N-(8- fluoro-4-methyl-3- quinolyl)pent-4-enamide

2.90 383 13 min Backpressure: 150 bar Flow rate: 60 ml/min GLS pump: 1ml/min EtOAc Detection: UV 235 nm Sample concentration: 17 mg/mL inMeOH/ EtOAc Injection: 200-600 μl

Biological Examples

Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (Vogels broth). After placing a (DMSO) solution of testcompound into a microtiter plate (96-well format), the nutrient brothcontaining the fungal spores is added. The test plates are incubated at24° C. and the inhibition of growth is determined photometrically 3-4days after application.

The following compounds of Tables E and F gave at least 80% control ofBotryotinia fuckeliana at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

E-1, E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13,E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-24, E-25,E-26, E-27, E-28, E-29, E-30, E-31, E-32, E-33, E-34, E-35, E-36, E-37,E-38, E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-49,E-50, E-51, E-52, E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61,E-63, E-64, E-65, E-66, E-68, E-69, E-70, E-71, E-72, E-73, E-74, E-75,E-76, E-77, E-78, E-79, E-80, E-81, E-82, E-83, E-84, E-85, E-86, E-87,E-88, E-92, E-93, E-94, E-95, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8,F-9, F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-19, F-20,F-21, F-22, F-23, F-24Fusarium culmorum/Liquid Culture (Head Blight)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofFusarium culmorum at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:

E-1, E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13,E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-24, E-25,E-26, E-27, E-28, E-30, E-31, E-32, E-33, E-34, E-35, E-36, E-37, E-38,E-39, E-40, E-41, E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-49, E-50,E-51, E-52, E-53, E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61, E-63,E-64, E-65, E-66, E-68, E-69, E-70, E-71, E-72, E-73, E-74, E-75, E-76,E-77, E-78, E-79, E-80, E-81, E-82, E-83, E-84, E-85, E-86, E-87, E-88,E-92, E-93, E-94, E-95, F-1, F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9,F-10, F-11, F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-19, F-20, F-21,F-22, F-23, F-24Fusarium culmorum/Wheat/Spikelet Preventative (Head Blight)

Wheat spikelets cv. Monsun are placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The spikelets are inoculated with a spore suspension of thefungus 1 day after application. The inoculated spikelets are incubatedat 20° C. and 60% rh under a light regime of 72 h semi darkness followedby 12 h light/12 h darkness in a climate chamber and the activity of acompound is assessed as percent disease control compared to untreatedwhen an appropriate level of disease damage appears on untreated checkspikelets (6-8 days after application).

The following compounds of Tables E and F gave at least 80% control ofFusarium culmorum at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:

E-1, E-2, E-5, E-8, E-10, E-19, E-20, E-21, E-25, E-28, E-32, E-35,E-37, E-38, E-39, E-40, E-41, E-43, E-44, E-45, E-47, E-48, E-50, E-51,E-53, E-55, E-56, E-57, E-58, E-59, E-60, E-63, E-64, E-66, E-68, E-69,E-71, E-74, E-77, E-78, E-80, E-81, E-82, E-83, E-84, E-86, E-87, E-88,E-92, F-1, F-2, F-4, F-6, F-7, F-8, F-9, F-11, F-12, F-13, F-14, F-19,F-20, F-21, F-23, F-24Glomerella lagenarium (Colletotrichum lagenarium)/Liquid Culture(Anthracnose)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is measuredphotometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofGlomerella lagenarium at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

E-1, E-2, E-3, E-4, E-5, E-6, E-7, E-8, E-9, E-10, E-11, E-12, E-13,E-14, E-15, E-16, E-17, E-18, E-19, E-20, E-21, E-22, E-23, E-24, E-25,E-26, E-28, E-31, E-32, E-33, E-34, E-35, E-36, E-37, E-38, E-39, E-40,E-41, E-42, E-43, E-44, E-45, E-46, E-47, E-48, E-50, E-51, E-52, E-53,E-54, E-55, E-56, E-57, E-58, E-59, E-60, E-61, E-64, E-65, E-66, E-68,E-69, E-70, E-71, E-72, E-73, E-74, E-75, E-76, E-77, E-78, E-79, E-80,E-81, E-82, E-83, E-84, E-85, E-86, E-87, E-92, E-93, E-94, E-95, F-1,F-2, F-3, F-4, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13, F-14,F-15, F-16, F-17, F-18, F-19, F-20, F-21, F-22, F-23, F-24Gaeumannomyces graminis/Liquid Culture (Take-all of Cereals)

Mycelial fragments of the fungus from cryogenic storage were directlymixed into nutrient broth (PDB potato dextrose broth). After placing a(DMSO) solution of test compound into a microtiter plate (96-wellformat), the nutrient broth containing the fungal spores is added. Thetest plates are incubated at 24° C. and the inhibition of growth isdetermined photometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofGaeumannomyces graminis at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

E-65, E-66, E-68, E-69, E-70, E-71, E-72, E-73, E-74, E-75, E-76, E-77,E-82, E-83, E-85, E-87, F-20

Monographella nivalis (Microdochium nivale)/Liquid Culture (Foot RotCereals)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofMonographella nivalis at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

E-1, E-3, E-5, E-6, E-7, E-9, E-10, E-11, E-12, E-13, E-15, E-17, E-18,E-20, E-22, E-23, E-24, E-26, E-27, E-28, E-30, E-32, E-36, E-37, E-39,E-40, E-41, E-43, E-46, E-50, E-51, E-52, E-53, E-55, E-56, E-57, E-58,E-59, E-60, E-61, E-62, E-64, E-65, E-66, E-68, E-69, E-71, E-72, E-74,E-76, E-77, E-78, E-80, E-82, E-83, E-84, E-86, E-87, E-93, E-94, E-95,F-3, F-5, F-6, F-7, F-8, F-9, F-10, F-12, F-13, F-14, F-15, F-16, F-17,F-18, F-20, F-21, F-22, F-23, F-24Mycosphaerella arachidis (Cercospora arachidicola)/Liquid Culture (EarlyLeaf Spot)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofMycosphaerella arachidis at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

Magnaporthe grisea (Pyricularia oryzae)/Liquid Culture (Rice Blast)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofMagnaporthe grisea at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development:

E-7, E-8, E-9, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18,E-19, E-20, E-21, E-22, E-23, E-24, E-25, E-26, E-27, E-28, E-29, E-30,E-31, E-32, E-33, E-34, E-35, E-36, E-37, E-38, E-39, E-40, E-41, E-42,E-43, E-44, E-45, E-46, E-47, E-48, E-49, E-50, E-51, E-52, E-53, E-54,E-55, E-56, E-57, E-58, E-59, E-60, E-61, E-63, E-64, E-65, E-66, E-68,E-70, E-71, E-72, E-73, E-74, E-75, E-76, E-77, E-79, E-80, E-81, E-82,E-83, E-87, E-88, F-1, F-2, F-3, F-5, F-6, F-7, F-8, F-9, F-10, F-11,F-12, F-13, F-14, F-15, F-16, F-17, F-18, F-23, F-24 Magnaporthe grisea(Pyricularia oryzae)/rice/leaf disc preventative (Rice Blast) Rice leafsegments cv. Ballila are placed on agar in a multiwell plate (24-wellformat) and sprayed with the formulated test compound diluted in water.The leaf segments are inoculated with a spore suspension of the fungus 2days after application. The inoculated leaf segments are incubated at22° C. and 80% rh under a light regime of 24 h darkness followed by 12 hlight/12 h darkness in a climate cabinet and the activity of a compoundis assessed as percent disease control compared to untreated when anappropriate level of disease damage appears in untreated check leafsegments (5-7 days after application).

The following compounds gave at least 80% control of Magnaporthe griseaat 200 ppm when compared to untreated control under the same conditions,which showed extensive disease development:

E-1, E-2, E-6, E-8, E-13, E-17, E-18, E-19, E-20, E-21, E-26, E-27,E-29, E-30, E-44, E-45, E-46, E-50, E-76, E-80, E-93, F-1, F-2, F-4,F-6, F-9, F-11, F-12, F-21

Pyrenophora teres/Barley/Leaf Disc Preventative (Net Blotch)

Barley leaf segments cv. Hasso are placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf segmens are inoculated with a spore suspension of thefungus 2 days after application. The inoculated leaf segments areincubated at 20° C. and 65% rh under a light regime of 12 h light/12 hdarkness in a climate cabinet and the activity of a compound is assessedas disease control compared to untreated when an appropriate level ofdisease damage appears in untreated check leaf segments (5-7 days afterapplication).

The following compounds of Tables E and F gave at least 80% control ofPyrenophora teres at 200 ppm when compared to untreated control underthe same conditions, which showed extensive disease development: F-3,F-20

Mycosphaerella graminicola (Septoria tritici)/Liquid Culture (Septoriablotch)

Conidia of the fungus from cryogenic storage are directly mixed intonutrient broth (PDB potato dextrose broth). After placing a (DMSO)solution of test compound into a microtiter plate (96-well format), thenutrient broth containing the fungal spores is added. The test platesare incubated at 24° C. and the inhibition of growth is determinedphotometrically 4-5 days after application.

The following compounds of Tables E and F gave at least 80% control ofMycosphaerella graminicola at 200 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:E-19, E-64, E-80, F-7, F-8, F-13

Sclerotinia sclerotiorum/Liquid Culture (Cottony Rot)

Mycelia fragments of a newly grown liquid culture of the fungus aredirectly mixed into nutrient broth (Vogels broth). After placing a(DMSO) solution of test compound into a microtiter plate (96-wellformat) the nutrient broth containing the fungal material is added. Thetest plates are incubated at 24° C. and the inhibition of growth isdetermined photometrically 3-4 days after application.

The following compounds of Tables E and F gave at least 80% control ofSclerotinia sclerotiorum at 20 ppm when compared to untreated controlunder the same conditions, which showed extensive disease development:

E-8, E-10, E-11, E-12, E-13, E-14, E-15, E-16, E-17, E-18, E-19, E-20,E-21, E-22, E-25, E-45, E-47, E-50, E-51, E-53, E-56, E-74, E-80, E-81,E-87, F-1, F-2, F-3, F-5, F-6, F-7, F-8, F-9, F-10, F-11, F-12, F-13,F-14, F-15, F-23

What is claimed is:
 1. A compound of formula (I):

wherein X is O or S; R₁ is hydrogen, halogen, methyl, methoxy or cyano;R₂ and R₃ are each independently hydrogen, halogen, methoxy or methyl;R₄ is hydrogen, halogen, cyano, C₁-C₄ alkoxy, C₁-C₄ alkyl, or C₃-C₄cycloalkyl, wherein the alkoxy, alkyl and cycloalkyl may be optionallysubstituted with 1 to 3 substituents independently selected fromhalogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy and C₁-C₃ alkylthio; R₅ and R₆are each independently selected from hydrogen, halogen, C₁-C₄ alkyl,C₁-C₄ alkoxy, C₁-C₄ haloalkoxy, C₁-C₄ alkylthio and C₁-C₄ haloalkylthio;or R₅ and R₆ together with the carbon atom to which they are attachedrepresent C═O, C═NOR_(c), C₃-C₅ cycloalkyl or C₂-alkenyl, wherein thecycloalkyl may be optionally substituted with 1 to 3 substituentsindependently selected from halogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxyand C₁-C₃ alkylthio, and wherein the alkenyl may be optionallysubstituted with 1 or 2 substituents independently selected from cyano,C₁-C₄ alkyl, fluoro and chloro; R₇ is hydrogen, cyano, —CHO, —C(═O)C₁-C₅alkyl, —CH(═NOR_(c)), —C(═NOR_(c))C₁-C₅ alkyl, C₁-C₅ alkyl, C₃-C₅cycloalkyl, C₂-C₅ alkenyl, C₃-C₅ cycloalkenyl, or C₂-C₅ alkynyl, whereinthe alkyl, cycloalkyl, alkenyl, alkynyl, cycloalkenyl may be optionallysubstituted with 1 to 4 substituents independently selected fromhalogen, cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, hydroxyl and C₁-C₃ alkylthio;R₈ and R₉ are each independently selected from hydrogen, halogen, C₁-C₄alkyl and C₁-C₄ alkoxy; or R₈ and R₉ together with the carbon atom towhich they are attached represent C═O, C═NOR_(c) or C₃-C₅ cycloalkyl,wherein the cycloalkyl may be optionally substituted with 1 to 3substituents independently selected from halogen, cyano, C₁-C₃ alkyl,C₁-C₃ alkoxy and C₁-C₃ alkylthio; each R₁₀ independently representshalogen, nitro, cyano, formyl, C₁-C₅ alkyl, C₂-C₅ alkenyl, C₂-C₅alkynyl, C₃-C₆ cycloalkyl, C₁-C₅ alkoxy, C₃-C₅ alkenyloxy, C₃-C₅alkynyloxy, C₁-C₅ alkylthio, —C(═NOR_(c))C₁-C₅ alkyl, or C₁-C₅alkylcarbonyl, wherein the alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy,alkenyloxy, alkynyloxy and alkylthio may be optionally substituted with1 to 5 substituents independently selected from halogen, C₁-C₃ alkyl,C₁-C₃ alkoxy, cyano and C₁-C₃ alkylthio; n is 0, 1, 2, 3, 4 or 5; eachR_(c) is independently selected from hydrogen, C₁-C₄ alkyl, C₂-C₄alkenyl, C₃-C₄ alkynyl, C₃-C₄ cycloalkyl(C₁-C₂)alkyl and C₃-C₄cycloalkyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl groupsmay be optionally substituted with 1 to 3 substituents independentlyselected from halogen and cyano; R₁₁ is hydrogen, halogen, methyl,methoxy or cyano; R₁₂ and R₁₃ are each independently selected fromhydrogen, halogen, methyl, methoxy or hydroxyl; and R₁₄ is hydrogen,C₁-C₅ alkyl, C₃-C₅ cycloalkyl, C₃-C₅ alkenyl, C₃-C₅ alkynyl or C₁-C₅alkoxy wherein the alkyl, cycloalkyl, alkenyl, alkynyl and alkoxy may beoptionally substituted with 1 to 4 substituents independently selectedfrom halogen, cyano, C₁-C₃ alkoxy, C₁-C₃ alkylsulfonyl and C₁-C₃alkylthio; or a salt, enantiomer or N-oxide thereof.
 2. A compoundaccording to claim 1 wherein R₁ is hydrogen, halogen, methyl or cyano.3. A compound according to claim 1 wherein R₂ and R₃ are eachindependently hydrogen, halogen or methyl.
 4. A compound according toclaim 1 wherein R₄ is hydrogen, halogen, cyano, C₁-C₄ alkoxy or C₁-C₄alkyl, wherein the alkoxy and alkyl may be optionally substituted with 1to 2 substituents independently selected from cyano, C₁-C₃ alkyl, C₁-C₃alkoxy, fluoro and chloro or 1 to 3 substituents independently selectedfrom fluoro and chloro.
 5. A compound according to claim 1 wherein R₅and R₆ are each independently selected from hydrogen, halogen, C₁-C₃alkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy and C₁-C₃ alkylthio; or R₅ and R₆together with the carbon atom to which they are attached represent C═O,C═NOR_(c) or C₂-alkenyl, wherein the alkenyl may be optionallysubstituted with 1 or 2 substituents independently selected from cyano,C₁-C₃ alkyl, fluoro and chloro.
 6. A compound according to claim 1wherein R₇ is hydrogen, C(═O)C₁-C₄ alkyl, —CH(═NOR_(c)),—C(═NOR_(c))C₁-C₄ alkyl, C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkenyl,C₃-C₅ cycloalkenyl or C₂-C₄ alkynyl, wherein the alkyl, cycloalkyl,alkenyl, alkynyl, cycloalkenyl may be optionally substituted with 1 to 2substituents independently selected from cyano, hydroxyl C₁-C₃ alkyl,C₁-C₃ alkoxy, fluoro and chloro or 1 to 3 substituents independentlyselected from fluoro and chloro.
 7. A compound according to claim 1wherein R₈ and R₉ are each independently selected from hydrogen, halogenand C₁-C₄ alkyl; or R₈ and R₉ together with the carbon atom to whichthey are attached represent C═O, or C₃-C₅ cycloalkyl, wherein thecycloalkyl may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro andchloro or 1 to 3 substituents independently selected from fluoro andchloro.
 8. A compound according to claim 1 wherein each R₁₀independently represents halogen, nitro, cyano, C₁-C₄ alkyl, C₂-C₄alkenyl, C₂-C₄ alkynyl, C₃-C₅ cycloalkyl, C₁-C₄ alkoxy, C₃-C₄alkenyloxy, C₃-C₄ alkynyloxy or C₁-C₄ alkylthio, wherein the alkyl,cycloalkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy andalkylthio may be optionally substituted with 1 to 2 substituentsindependently selected from cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro andchloro or 1 to 3 substituents independently selected from fluoro andchloro; n is 0, 1, 2, 3 or
 4. 9. A compound according to claim 1 whereinR₁₁ is hydrogen, fluoro, chloro or methyl; R₁₂ and R₁₃ are eachindependently selected from hydrogen, fluoro, chloro or methyl; and R₁₄is hydrogen, C₁-C₄ alkyl, C₃-C₅ cycloalkyl, C₃-C₄ alkenyl, C₃-C₄ alkynylor C₁-C₄ alkoxy, wherein the alkyl, cycloalkyl, alkenyl, alkynyl andalkoxy may be optionally substituted with 1 to 3 substituentsindependently selected from halogen, C₁-C₃ alkoxy and C₁-C₃ alkylthio.10. A compound according to claim 1 wherein X is O or S; R₁ is hydrogen,fluoro, chloro or methyl; R₂ and R₃ are each independently hydrogen,fluoro, chloro or methyl; R₄ is hydrogen, fluoro, C₁-C₃ alkoxy or C₁-C₃alkyl, wherein the alkoxy and alkyl may be optionally substituted with 1to 2 substituents independently selected from cyano, C₁-C₂ alkoxy,fluoro and chloro or 1 to 3 substituents independently selected fromfluoro and chloro; R₅ and R₆ are each independently selected fromhydrogen, fluoro, chloro, C₁-C₂ alkyl, C₁-C₃ alkoxy and C₁-C₂haloalkoxy; or R₅ and R₆ together with the carbon atom to which they areattached represent C═NOR_(c) or C₂-alkenyl, wherein the alkenyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom C₁-C₂ alkyl and fluoro; R₇ is hydrogen, —CH(═NOR_(c)),—C(═NOR_(c))C₁-C₂ alkyl, C₁-C₄ alkyl, C₃-C₄ cycloalkyl, C₂-C₃ alkenyl orC₂-C₄ alkynyl, wherein the alkyl, cycloalkyl, alkenyl and alkynyl may beoptionally substituted with 1 to 2 substituents independently selectedfrom cyano, C₁-C₃ alkyl, C₁-C₃ alkoxy, chloro and fluoro or 1 to 3fluoro substituents; R₈ and R₉ are each independently selected fromhydrogen, fluoro and C₁-C₂ alkyl; or R₈ and R₉ together with the carbonatom to which they are attached represent C₃-C₄ cycloalkyl, wherein thecycloalkyl may be optionally substituted with 1 to 2 substituentsindependently selected from C₁-C₂ alkyl, fluoro and chloro; each R₁₀independently represents fluoro, chloro, bromo, C₁-C₃ alkyl, C₃-C₅cycloalkyl, C₁-C₂ alkoxy or C₁-C₂ alkylthio, wherein the alkyl,cycloalkyl, alkoxy and alkylthio may be optionally substituted with 1 to2 substituents independently selected from C₁-C₂ alkyl, C₁-C₂ alkoxy andfluoro or 1 to 3 fluoro substituents; n is 0, 1, 2 or 3; each R_(c) isindependently selected from hydrogen, C₁-C₂ alkyl, C₂-C₃ alkenyl, C₃-C₄alkynyl, wherein the alkyl, alkenyl and alkynyl groups may be optionallysubstituted with 1 to 3 fluoro substituents; R₁₁ is hydrogen, fluoro orchloro; R₁₂ and R₁₃ are each independently hydrogen or fluoro; and R₁₄is hydrogen, methyl, ethyl, C₃-C₄ cycloalkyl, C₃-C₄ alkenyl, C₃-C₄alkynyl or C₁-C₃ alkoxy, wherein the alkyl, cycloalkyl, alkenyl, alkynyland alkoxy may be optionally substituted with 1 to 3 fluoro substituentsor a C₁-C₂ alkoxy; or a salt, enantiomer or N-oxide thereof.
 11. Acompound according to claim 1 wherein X is O or S; R₁ is hydrogen,fluoro or methyl; R₂ and R₃ are each independently hydrogen, fluoro ormethyl; R₄ is hydrogen, fluoro, C₁-C₃ alkoxy or C₁-C₂ alkyl, wherein thealkoxy and alkyl may be optionally substituted with 1 to 2 substituentsindependently selected from C₁-C₂ alkoxy, and fluoro or 1 to 3 fluorosubstituents; R₅ is hydrogen, fluoro or methyl; R₆ is hydrogen, fluoro,methyl, C₁-C₃ alkoxy or C₁-C₂ haloalkoxy; or R₅ and R₆ together with thecarbon atom to which they are attached represent C₂-alkenyl, wherein thealkenyl may be optionally substituted with 1 to 2 substituentsindependently selected from methyl and fluoro; R₇ is hydrogen,—C(═NOR_(c))C₁-C₂ alkyl, C₁-C₄ alkyl, cyclopropyl, C₂-C₃ alkenyl orC₂-C₃ alkynyl, wherein the alkyl, cyclopropyl, alkenyl and alkynyl maybe optionally substituted with 1 to 2 substituents independentlyselected from cyano, methyl, C₁-C₂ alkoxy, chloro and fluoro or 1 to 3fluoro substituents; R₈ is hydrogen or fluoro; R₉ is hydrogen, fluoro ormethyl; each R₁₀ independently represents fluoro, chloro, C₁-C₂ alkyl,cyclopropyl, or C₁-C₂ alkoxy, wherein the alkyl, cyclopropyl and alkoxymay be optionally substituted with 1 to 2 substituents independentlyselected from methyl, methoxy and fluoro or 1 to 3 fluoro substituents;n is 0, 1 or 2; each R_(c) is independently selected from hydrogen andC₁-C₂ alkyl, wherein the alkyl group may be optionally substituted with1 to 3 fluoro substituents; R₁₁ is hydrogen or fluoro; R₁₂ and R₁₃ areboth hydrogen; and R₁₄ is hydrogen, methyl, ethyl, cyclopropyl, allyl,propargyl or methoxy, wherein the methyl and ethyl may be optionallysubstituted with 1 to 3 fluoro substituents or a methoxy; or a salt,enantiomer or N-oxide thereof.
 12. A compound according to claim 1wherein X is O or S; R₁ is hydrogen or fluoro; R₂ is hydrogen and R₃ ismethyl; or R₂ is methyl and R₃ is hydrogen; or R₂ and R₃ are bothhydrogen; R₄ is hydrogen or C₁-C₂ alkyl, wherein the alkyl may beoptionally substituted with 1 methoxy substituent or 1 to 3 fluorosubstituents; R₅ is hydrogen; R₆ is hydrogen, methyl or C₁-C₃ alkoxy; R₇is C₁-C₄ alkyl, cyclopropyl or C₂-C₃ alkenyl, wherein the alkyl,cyclopropyl, and alkenyl may be optionally substituted with 1 to 2substituents independently selected from methyl, methoxy, chloro andfluoro or 1 to 3 fluoro substituents; R₈ is hydrogen or fluoro; R₉ ishydrogen or fluoro; each R₁₀ independently represents fluoro, chloro orC₁-C₂ alkyl, wherein the alkyl may be optionally substituted with 1methoxy substituents or 1 to 3 fluoro substituents; n is 0, 1 or 2; R₁₁is hydrogen or fluoro; and R₁₂, R₁₃ and R₁₄ are all hydrogen; or a salt,enantiomer or N-oxide thereof.
 13. A compound according to claim 1wherein X is O.
 14. A composition comprising a fungicidally effectiveamount of a compound of formula (I) as defined in claim
 1. 15. Acomposition according to claim 14, wherein the composition furthercomprises at least one additional active ingredient and/or a diluent.16. A method of combating, preventing or controlling phytopathogenicdiseases which comprises applying to a phytopathogen, to the locus of aphytopathogen, or to a plant susceptible to attack by a phytopathogen,or to propagation material thereof, a fungicidally effective amount of acompound of formula (I) as defined in any of claims 1-13 or acomposition comprising a fungicidally effective amount of a compound offormula (I) as defined in claim 1.